WO2005029201A1 - Holographic recording medium, holographic recording method, and holographic information medium - Google Patents

Holographic recording medium, holographic recording method, and holographic information medium Download PDF

Info

Publication number
WO2005029201A1
WO2005029201A1 PCT/JP2004/013591 JP2004013591W WO2005029201A1 WO 2005029201 A1 WO2005029201 A1 WO 2005029201A1 JP 2004013591 W JP2004013591 W JP 2004013591W WO 2005029201 A1 WO2005029201 A1 WO 2005029201A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
holographic recording
recording medium
holographic
group
Prior art date
Application number
PCT/JP2004/013591
Other languages
French (fr)
Japanese (ja)
Inventor
Toshihisa Takeyama
Original Assignee
Konica Minolta Medical & Graphic, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2004058640A external-priority patent/JP2005181953A/en
Priority claimed from JP2004072139A external-priority patent/JP4466141B2/en
Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to EP04773235A priority Critical patent/EP1666988A4/en
Publication of WO2005029201A1 publication Critical patent/WO2005029201A1/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H2001/026—Recording materials or recording processes
    • G03H2001/0264—Organic recording material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer

Definitions

  • the present invention relates to a holographic recording medium capable of large-capacity and high-speed transfer, and further relates to a holographic recording method and holographic information on which information is recorded.
  • a recording method in this holographic recording for example, a recording method using a holographic recording medium in which transparent substrates are arranged on both sides of a holographic recording layer (for example, US Pat. No. 5,719,691) and A recording method using a holographic recording medium having a reflective surface disposed on one side of a holographic recording layer (for example, JP-A-2002-123949) and the like have been proposed.
  • Such a holographic recording medium records information by changing a refractive index in a holographic recording layer in the medium by holographic exposure, and detects a change in a refractive index in the recorded medium.
  • the basic principle is that information is reproduced by reading.
  • the holographic recording layer is made of a material using an inorganic material (for example, UK Patent No. 9,929,953), and is structured by light. (For example, Japanese Patent Application Laid-Open No. H10-340479) or a material using diffusion polymerization of a photopolymer (for example, US Pat. No. 4,942,112).
  • the material using the photopolymer described in Patent Document 5 uses a volatile solvent when producing the recording layer forming composition, so that the thickness of the recording layer is at most about 150 ⁇ . Is restricted to In addition, the volume shrinkage of 4-10% caused by polymerization adversely affected the reliability of reproducing the recorded information.
  • a holographic recording layer forming composition utilizing the same (for example, U.S. Pat. No. 5,759,721).
  • the recording layer-forming composition is a liquid substance other than the monomer that causes photo-induced thione polymerization
  • the island-shaped monomer formed by photo-polymerization of the monomer in the recording layer by holographic exposure is used.
  • drawbacks such as the possibility that the part may move, and the volume of the liquid substance expands due to changes in the environmental temperature inside the device.
  • radical polymerization is used for recording in holographic exposure, and a binder is formed after the formation of the medium in order to retain the radically polymerizable monomer before the exposure (for example, a thread-forming material (for example, U.S. Pat. No. 6,103,454) has been proposed.
  • a thread-forming material for example, U.S. Pat. No. 6,103,454
  • Use of such a composition can increase the thickness of the holographic recording layer and reduce volume shrinkage. Can be done, but it is still not enough.
  • a hologram recording photosensitive composition using a binder having a high degree of polymerization in advance instead of a binder-forming compound (for example, International Publication No. 3Z081)
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a holographic recording medium, a holographic recording method, a holographic recording method, and a holographic recorded holographic recording medium having high sensitivity and excellent storage stability. Decide to provide information media.
  • one embodiment of the present invention provides: (1) a binder-forming compound, a compound having an ethylenically unsaturated bond between the first base material and the second base material, A holographic recording medium having a holographic recording layer containing a photopolymerization initiator capable of initiating a polymerization reaction of a compound having the formula (I) and a sensitizing dye capable of spectrally sensitizing the photopolymerization initiator.
  • the binder-forming compound comprises a combination of at least one compound selected from the following (1) to (8):
  • the content of the compound having an ethylenically unsaturated bond is 11 to the entire composition.
  • a holographic recording medium wherein the photopolymerization initiator contains at least a compound represented by the following general formula (1).
  • A represents an unsubstituted or alkyl-substituted cyclopentagel group
  • B represents an unsubstituted or substituted arene group
  • X— represents a fluorine atom-containing anion.
  • the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, or (7) a compound having an oxysilane group and a compound having a mercaptan group.
  • the holographic recording medium according to the above (1) characterized by the following.
  • the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, and the compound having an isocyanate group has three or more isocyanate groups in the compound. 0 mass% or more 65 mass.
  • the compound having an isocyanate group containing at least 3 isocyanate groups in an amount of 30% by mass or more and 65% by mass or less based on the entire compound having the isocyanate group is used.
  • the holographic recording medium according to (3), wherein the compound having an isocyanate group has a molecular weight of 200 to 500.
  • the compound having a hydroxyl group is a compound having two or more hydroxyl groups in a molecule having a molecular weight of 100 to 2,000.
  • the compound having an ethylenically unsaturated bond includes a compound having a (meth) acryloyl group in a molecule.
  • a compound having a refractive index of at least 1.55 or more is 50% by mass based on the whole compound having an ethylenically unsaturated bond. / 0 to 10.0% by mass.
  • a holographic recording medium according to (I) A holographic recording medium according to (I).
  • the thickness of the first base material is D1
  • the thickness of the second base material is D2
  • the thickness of the holographic recording layer is Dh.
  • the thickness Dh of the holographic recording layer is 200 ⁇ or more and 2.0 mm or less, 0.15 Dh / (D 1 + D 2) ⁇ 2.0, and the relationship of D 1 ⁇ D 2 is satisfied.
  • the first base material is transparent, and an antireflection treatment is performed on a surface of the first base material opposite to a surface in contact with the holographic recording layer.
  • the holographic recording medium according to the above (1).
  • the holographic recording medium according to the above (1) wherein the material of the first base material is glass.
  • the holographic recording medium according to (1) wherein a reflective layer having a reflectance of 70% or more is laminated on the second base material.
  • the holographic recording medium according to (1) wherein the holographic recording medium has a disk shape or a card shape. It is a recording media.
  • the binder-forming compound is exposed before the holographic recording medium is subjected to holographic exposure.
  • Holographic exposure was performed by injecting information light and reference light from the first substrate side based on the information, and the photopolymerization initiator was activated.
  • the holographic recording method is characterized in that information is recorded on a holographic recording medium by diffusion-polymerizing a compound having an ethylenically unsaturated bond with the active species in a holographic recording layer.
  • the whole holographic recording medium may be further stabilized by irradiating heat.
  • a holographic recording method as described in (14) above which is characterized by the following.
  • the first base material side may be used based on information to be recorded on the holographic recording medium.
  • the holographic exposure is performed by injecting information light and reference light from the holographic recording medium, the photopolymerization initiator is activated, and the compound having an ethylenically unsaturated bond is diffused and polymerized by the active species, whereby information is recorded on the holographic recording medium.
  • an embodiment of the present invention provides a holographic information recording medium in which information is recorded on the holographic recording layer in the holographic recording medium according to (1).
  • the holographic information recording layer comprises a region mainly composed of a binder formed from the binder-forming compound and a compound having an ethylenically unsaturated bond.
  • FIG. 1 is a schematic diagram showing the principle of a measuring device used for measuring a shrinkage ratio.
  • the holographic recording medium of the present invention is a holographic recording medium in which a holographic recording layer is sandwiched between a first base material and a second base material, wherein the holographic recording layer has a compound having an isocyanate group and a hydroxyl group.
  • a compound having an isocyanate group and a compound having an amino group, a compound having a phenolic group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a mercaptan Compounds having a group, compounds having a vinyl group and compounds having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxsilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetanol, and bicyclic acetal Lactone, cyclic orthoester, compound having at least one group selected from cyclic carbonate in the molecule and at least one kind of binder selected from thermal cationic polymerization initiators
  • the photopolymerization initiator capable of initiating the polymerization reaction of the compound having an ethylenically unsaturated bond is at least a compound represented by the general formula (I). It is characterized by containing the compound represented by 1).
  • the binder-forming compound refers to a precursor that is not a polymer as a binder when the recording composition is prepared, and will be described later in detail by using such a binder-forming compound. It is possible to prevent the recording medium from shrinking before and after the above-described holodographic exposure, and to increase the thickness of the recording layer when the holographic recording medium is manufactured.
  • the binder-forming compound of the present invention does not polymerize or cross-link between the binder-forming compounds. Or by polymerizing or crosslinking after holographic exposure to form a binder.
  • the binder-forming compound include a compound having an isocyanate group and a compound having a hydroxyl group, a compound having an isocyanate group and a compound having an amino group, a compound having a carposimido group and a carboxyl group, and an unsaturated ester group.
  • At least one combination may be used as appropriate, and further, a compound having an isocyanate group and a compound having a hydroxyl group, which can be polymerized or cross-linked to a binder under mild conditions in the above selection.
  • a compound having an oxysilane group and a compound having a mercaptan group is more preferable.
  • the compound having an isocyanate group used for crosslinking the compound having an isocyanate group and the compound having a hydroxyl group used in the present invention can be used without any particular limitation, and is a photopolymerization component described in detail above.
  • a compound having two or more isocyanate groups in a molecule is more preferable.
  • a recording medium it is produced by sandwiching a recording composition that is liquid at room temperature or liquid at a temperature of 100 ° C. or less with a predetermined thickness between two substrates. A liquid or a compound having a melting point of 100 ° C. or less is more preferable.
  • Such a compound having a sosinate group include, for example, 1,8-diisocyanate-41-isocyanate methylenoloctane, 2-isocyanateethyl-2,6-diisocyanate, and benzene-1-one , 3,5-triisocyanate, 1-methinolebenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene -2,4,6-triisocyanate, diphenylmethane-2,4 , 4'-triisomethane, triphenylmethane-1,4'-triisocyanate, bis (isocyanatotolyl) phenyl / lemethane, dimethylene diisocyanate, tetramethylene diisocyanate , Hexanemethylene diisocyanate, 2,2-dimethy ⁇ / pentanediisocyanate, 2,2,4-trimethyolepentanediisocyanate
  • an isocyanate compound having three or more isocyanate groups in a molecule and the proportion of the isocyanate group in the compound is 30% by mass or more and 65% by mass or less is used. It is more preferable to use it because the shrinkage of the recording medium before and after the holographic exposure described later can be prevented.
  • Such an isocyanate compound having three or more isocyanate groups in the molecule and in which the proportion of the isocyanate group occupying the compound is 30% by mass or more and 65% by mass or less in the compound is a compound that satisfies this condition.
  • a holographic recording medium in which a recording layer composed of a holographic recording composition described in detail below is laminated, and the holographic information used after the recording is completed.
  • Media like CDs and DVs, can have a variety of ambient temperatures under fluorescent lights, windowsills, or left behind. Therefore, it is preferable that the coloring of the recording layer is suppressed under various conditions, and to suppress the coloring in this way, among the above-mentioned compounds, the aliphatic isocyanate compound is more preferable.
  • the binder may be formed by self-crosslinking of the compound having an isocyanate group, which is an essential component described above.
  • the isocyanate compound described in detail above is required. It is preferable to form a binder by a cross-linking reaction with a compound having a functional group that reacts with the isocyanate group in the molecule. Examples of such a compound that can react with the isocyanate compound include a compound having a hydroxyl group in the molecule. And compounds having a primary or secondary amino group, and compounds having an enamine structure.
  • a compound having a hydroxyl group is preferable as a compound capable of reacting with the isocyanate compound, and a compound having two or more aliphatic alcoholic hydroxyl groups in the molecule is more preferable.
  • a liquid composition at room temperature or a liquid composition at a temperature of 100 ° C. or less is provided with a predetermined thickness between two substrates. Since it is produced by being sandwiched between layers, compounds that are liquid at room temperature or have a melting point of 100 ° C or less are often used. Is more preferable.
  • Such compounds having two or more alcoholic hydroxyl groups in the molecule include, for example, diethylene glycol ⁇ triethylene glycol ⁇ /, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2,2-dimethyl-1 , 3-propanediole, 2,2-getyl-1,3-propanediol, 2-butynole-2-ethyneol 1,3_propanediole, 1,2-butanediole, 1,4-butanediol , Polytetramethylene glycol, 1,5-pentanedionole, 2-methyl-2,4- ⁇ pentanediole, 3-methinole-1,5-pentanediol, 1,6-hexanediol, 2-ethynol-1, 3-hexanediolone, 2,5-dimethyl-2,5-hexanediol, 1,10-de
  • the molecular weight of a compound having two or more aliphatic alcoholic hydroxyl groups in a molecule may be a compound having a volatility of the compound itself, a compound having an ethylenically unsaturated bond, a compound having a cationically polymerizable functional group, or a photopolymerization.
  • the molecular weight is 100 or more and 200 or less.
  • the amount of the compound having two or more aliphatic alcoholic hydroxyl groups in the molecule cannot be specified unconditionally by the type and amount of the isocyanate compound, which is an essential component described above, but the amount of the compound having an isocyanate group
  • the mole number of the isocyanate group in the holographic recording composition of the compound is N [mo 1], and the alcoholic water.
  • the mole number of the hydroxyl group in the holographic recording composition of the compound is M [mo 1 ], It is usually 0.5 ⁇ NZM ⁇ 2.0, and more preferably 0.7 ⁇ N / M ⁇ 1.5 in terms of compatibility and control of crosslinking reaction. I like it.
  • the urethane bond when a compound having an isocyanate group and a compound having two or more alcoholic hydroxyl groups in a molecule are reacted to form a urethane bond, the urethane bond may be reacted at a low temperature. It is preferable to add a known organic metal compound such as tin or lead as a curing catalyst.
  • the compound having an oxysilane group or the compound having a mercaptan group in a molecule used in forming a binder by polymerizing a compound having an oxysilane group and a compound having a mercaptan group a known crosslinkable compound is particularly preferable.
  • the recording composition which is liquid at room temperature or liquid at a temperature of 100 ° C or less is used. Since it is produced by sandwiching it with a predetermined thickness between two substrates, a compound that is liquid at room temperature or has a melting point of 100 ° C. or less is preferable, and two oxysilane groups or mercaptan groups are more preferable. Compounds having the above are more preferred.
  • Specific examples of the above-mentioned compound having an oxysilane group include aliphatic polyglycidyl ether, polyalkylene glycol diglycidyl ether, tertiary carboxylic acid monoglycidyl ether, and polycondensate of bisphenol A and epichlorohydrin.
  • the compounds described in “Chemical Products of 112,900”, Kagaku Kogyo Nippo Co., Ltd., pp. 778-787 can also be suitably used, and such compounds having an oxysilane group in the molecule can be used.
  • the substances may be used in combination of two or more if necessary.
  • Examples of the compound having a mercaptan group include, for example, thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolate, sodium thioglycolate, methyl thioglycolate, octyl thioglycolate, and methoxybutyl thioglycolate.
  • These thiol-containing compounds may be used alone or in combination of two or more.
  • a prensted base or a Lewis base in order to perform polymerization under milder conditions.
  • bases include, for example, pyridine, piperidine, dimethylaniline, 2,4,6-tris (dimethylamino Amines such as methyl) benzene and 2,4,6-tris (dimethylaminomethyl) phenol.
  • an unsubstituted or alkyl-substituted cyclopentenyl group represented by A in the formula is used.
  • the one bonded to the cycle pentagenenyl group is hydrogen or an alkyl group.
  • the number of alkyl groups mentioned here is 0 to 5 with respect to the pentagenenyl group having a mouth, and the alkyl group is preferably a straight-chain, branched or cyclic one having 11 to 12 carbon atoms.
  • the unsubstituted or substituted arylene group represented by B is a non-substituted or substituted arylene group having at least a benzene ring such as benzene, naphthalene, anthracene, phenanthrene, thalicene, pyrene, triphenylene, perylene or fluorene.
  • a compound having a substituent or a substituent examples include a straight-chain, branched or cyclic alkyl group having 11 to 12 carbon atoms, _OR, -COR, -COOR, and the like.
  • R represents a linear, branched or cyclic alkyl group having 11 to 12 carbon atoms.
  • the anion represented by X— includes halogen, nitrate ion, hexafenoleo antimonate, hexafenoleo phosphate, triflate, tetrafluoroborate, and pentafluorohydroxyantimonate. And the like.
  • Such a compound represented by the general formula (1) include, for example, ( ⁇ 6 -m-xylene) (775-cyclopentagenenyl) iron (1 +) tetrafluoroborate, ( ⁇ 6-0-xylene) (5-cyclopentagenenyl) iron (1+) triflate, ( ⁇ 6-o-xylene) ( ⁇ 5-cyclopentagenenyl) iron (1+) hexafluoroantimo , (776- ⁇ -xylenes).
  • the aion containing a fluorine atom as the aion represented by ⁇ _ in the formula represents the stability of the complex itself and the recording layer. It is preferable because the liquid stability at the time of preparing the forming composition and the radical can be more effectively generated as a photopolymerization initiator.
  • the photopolymerization initiator for photopolymerizing the compound having an ethylenic unsaturated bond of the present invention includes, in addition to the compound represented by the general formula (1) described in detail above, benzoin and benzoin, which are conventionally known.
  • carbonyl compounds such as benzophenone, azo compounds such as azobisisobutyronitrile, sulfur compounds such as dibenzothiazolyl sulfide, peroxides such as benzoyl peroxide, 2-tribromomethanesulfonyl- Halides such as pyridine, quaternary ammonium salts or onium compounds such as substituted or unsubstituted diphenylbenzene salts and triphenylsulfonium salts, 2,2-bis (o-chlorophenyl) —4 Photopolymerization of bisimidazole compounds such as 1,4,5,5, -tetrapheninolebiimidazole and metal ⁇ complexes such as titanocene complexes
  • An initiator may be used in combination, and the wavelength of an exposure light source used for holographic exposure described later and the wavelength of a laser light source used for holographic exposure of the photopolymerization initiator may be used.
  • the sensitizing dye for sensitizing the spectral wavelength of the photopolymerization initiator used here, various dyes used in the art can be mentioned.
  • Various colorants such as a compound, a porphyrin derivative, a phthalocyanine derivative and a pyromethene derivative may be used alone or in combination of two or more as needed.
  • photopolymerization initiators or sensitizing dyes include, for example, US Pat. Nos. 5,027,436, 5,096,790, 5,147,758, 5, Nos. 204, 467, 5, 256, 520, 6, 01 1, 180, European Patent Nos. 255, 486, 256, 981, 277, 915, 318, 893, Nos.
  • the photopolymerization initiator for photopolymerizing the compound having an ethylenically unsaturated bond described above depends on the molecular weight of the photopolymerization initiator and the ratio of the ethylenically unsaturated bond in the compound having an ethylenically unsaturated bond. Although it cannot be unconditionally determined, it is usually preferred to use 0.01 to 25 parts by mass of the compound having an ethylenically unsaturated bond.
  • a sensitizing dye capable of spectrally sensitizing a photopolymerization initiator cannot be unconditionally defined by the molecular weight of the dye itself or the molar extinction coefficient, but is usually 0.01 to 25 to the photopolymerization initiator.
  • the compound having an ethylenically unsaturated bond has a refractive index higher or lower than that of the binder-forming compound.
  • Such compounds having a (meth) acryloyl group having a refractive index of 1.55 or more generally include, in the molecule, hetero atoms such as nitrogen, oxygen, sulfur and phosphorus, chlorine, bromine and boron.
  • hetero atoms such as nitrogen, oxygen, sulfur and phosphorus, chlorine, bromine and boron.
  • Compounds having a divalent or higher valence such as halogen atoms such as silicon or aromatic rings are mentioned.
  • Such compounds include paracumylphenoxhetylene glycol acrylate and paracumylphenoxyethylene glycol meta- Acrylate, hydroxylated, 0—phenylphenol acrylate, hydroxyxylated) 3—naphthol acrylate, triblemofenyl acrylate, trypnole mophenyl methacrylate, trydophenyl methacrylate, polyethylene Oxide modified tetrapromobisphenol A diacrylate, Ethylene oxide-modified tetrabromobisphenol A dimethatalylate, bis (4-methacryloylthiophenyl) sulfide, JP-A-6-310132, JP-A-200-344444 And compounds having a fluorene skeleton described in JP-A-2003-29604 and the like.
  • the purpose of providing a refractive index difference between the binder formed from the binder-forming compound and the diffusion polymer of the compound having an ethylenically unsaturated bond is not hindered.
  • (Meta) having a refractive index of less than 1.55 for the purpose of adjusting the compatibility and viscosity when preparing the holographic recording layer composition and controlling diffusion polymerization during holographic exposure.
  • a compound having an atariloyl group may be further added. Examples of such a compound having a (meth) acryloyl group include substituted or unsubstituted phenol and norphenol as a compound having one (meth) atalyloyl group.
  • (meth) acrylate of 2-ethylhexanol and (meth) acrylate of alkylene oxide adducts of these alcohols.
  • Compounds having two (meth) acryloyl groups include substituted or unsubstituted bisphenol A, bisphenol F, fluorene and di (meth) acrylate of isocyanuric acid, as well as alkylene oxide addition of these alcohols.
  • Compounds having three (meth) acryloyl groups include pentaerythritol, trimethylolpropane and tri (meth) atalylate of isocyanuric acid, and tri (meth) acrylate of an alkylene oxide adduct of these alcohols.
  • Examples of the compound having four or more (meth) atalyleinole groups include pentaerythritol and dipentaerythritol poly (meth) atalylate.
  • a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain, is appropriately selected in the present invention.
  • a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain, is appropriately selected in the present invention.
  • a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain
  • the compounds having an ethylenically unsaturated bond in the molecule described above may be used alone or in combination of two or more, and usually at least 1.0% by mass in the holographic recording composition. , 50% by mass or less, and more preferably 4.0% by mass or more, 40% by mass or less.
  • the compound having an ethylenically unsaturated bond is formed by diffusion polymerization of a compound having an ethylenically unsaturated bond to form a polymer having a high refractive index
  • the compound having a refractive index of 1.55 or more as described above is usually preferably contained in an amount of 50 to 100% by mass, and more preferably 60 to 100% by mass.
  • the first base material and the second base material used for the recording medium of the present invention are transparent and do not cause expansion or contraction or bending at the ambient temperature of use, and are incompatible with the above-mentioned recording composition.
  • Any active material can be used without particular limitation.
  • a substrate include quartz glass, soda glass, potash glass, lead crystal glass, borosilicate glass, aluminosilicate glass, titanium crystal glass, and crystallized glass.
  • Various resins such as glass such as polycarbonate, polyimide such as polycarbonate, polyacetal, polyarylate, polyetheretherketone, polysulfone and polyethersulfone, polyamide-amide-polyetherimide, polyamide, and cyclic olefin ring-opening polymer. Can be mentioned.
  • the information light and the reference light are considered from the viewpoints of thickness fluctuation with respect to environmental temperature and humidity during holographic exposure, gas permeability, and light transmittance of the light source wavelength used during holographic exposure.
  • the material of the first base material on the incident side is more preferably glass.
  • the second substrate is preferably made of glass, but if the holographically recorded information is read out by a CCD, a device provided with a focus correction mechanism may be used to expand or contract the thickness or thickness.
  • a substrate made of resin may be used instead of a substrate such as glass whose fluctuation is suppressed.
  • the transmittance of light incident on the first substrate on the side where the information light and the reference light are incident is preferably 70% or more, and more preferably 80% or more of the light reaching the holographic recording layer. This is more preferable because of low loss of the resin.
  • an anti-reflection treatment is applied to the first substrate surface opposite to the surface on which the holographic recording layer is laminated.
  • the treatment is not particularly limited as long as the refractive index of the first substrate is also low, but for example, inorganic metals such as AlF3, MgF2, AlF3'MgF2, and CaF2
  • Organic fluorine such as fluoride, vinylidene fluoride, homopolymers, copolymers, graft polymers, block polymers containing fluorine atoms such as Teflon (R), and modified polymers modified with functional groups containing fluorine atoms Compounds and the like are preferable because they have a lower refractive index than those described in detail above as the base material.
  • the method of providing a layer made of a fluorine-based compound on a base material cannot be unequivocally determined depending on the type of the support-fluorine-based compound, but a sol-gel method, a vacuum evaporation method, and a sputtering method
  • a known method such as a CVD method or a coating method, or a method described in JP-A-7-27902, JP-A-2001-123264, JP-A-2001-264509 or the like can be appropriately selected and used. .
  • Such an antireflection layer cannot be unconditionally defined by the surface treatment or material of the base material, but is usually in the range of 0.001 to 20 and preferably in the range of 0.005 to 10 um.
  • a second base material holographic recording layer is laminated on a recording medium such as used in a holographic recording / reproducing apparatus described in JP-A-2002-123949, WO 99/57719, and the like. It is preferable that a reflection layer is provided on the surface or on the opposite surface. When such a reflection layer is provided, the reflectance is preferably set to 70% or more with respect to the wavelength of the light to be reflected. % Is more preferable.
  • the material of such a reflective layer is not particularly limited as long as a desired reflectance can be obtained.
  • the layers can be laminated by providing a thin film of a metal or the like on the surface of the substrate.
  • a metal thin film for example, to form such a reflective layer, it can be laminated as a metal thin film, a metal single crystal or a polycrystal by a known method such as a vacuum deposition method, an ion plating method, and a sputtering method.
  • the metals used for laminating the metal thin film include anolemmium, dumbbell, antimony, indium, selenium, tin, tantalum, chromium, lead, gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, Metals such as manganese, tungsten, and palladium can be used alone or in combination of two or more.
  • the thickness of the metal thin film layer may be any thickness as long as a desired reflectance can be obtained,
  • any one of them is used.
  • a physical pattern may be formed on one surface of the substrate, and such a pattern or a forming method is described in, for example, JP-A-2003-178564, JP-A-2003-228885. No. 2003-33 1464, No. 2004-126306, No. 2004-126040, No. 2004-126041, No. 2004-1 273 79, No. 62, 100, U.S. Patent Publication No. 2004/0042375, 2004/006 7419, and the like can be appropriately selected and formed.
  • a recording medium with a high storage capacity can be manufactured by making the holographic recording layer as thick as possible.
  • the thickness of the first base material is Dl
  • the thickness of the second base material is D2
  • the thickness of the thick recording layer is Dh
  • the thickness of the holographic recording layer cannot be increased, or even if the thickness of the recording layer is increased, the thickness of the base material increases.
  • the entire recording medium becomes thick.
  • the mass of the recording medium alone is heavy, which may cause a load on the drive system of the apparatus, which is not preferable.
  • Dh / (D 1 + D 2)> 2.0 it is possible to reduce the thickness of the recording medium while securing the thickness of the recording layer.
  • the thickness of the recording layer becomes thicker, the surface accuracy of the recording medium, the thickness unevenness of the recording layer at the operating temperature, the thickness fluctuation of the recording layer when unexpected stress is applied, and the first base material.
  • the second substrate may be displaced, which is not preferable.
  • the relation between the thickness D2 of the second base material is D1 ⁇ D2, and in order to ensure the flatness of the recording medium, the ratio of the thickness of D1 to D2 is 0. More preferably, it is in the range of 20 ⁇ D1 / D2 ⁇ 1.00.
  • the thickness D h of the holographic recording layer cannot be determined unconditionally due to the diffraction efficiency, dynamic range, spatial resolution, etc. of the recording layer, but it is usually 200 ⁇ or more.
  • the recording layer may have uneven thickness.
  • the shape of the recording medium is not particularly limited as long as it is suitable for the holographic recording / reproducing apparatus used for the recording medium.
  • US Pat. Disc-shaped ones are preferred for use in the apparatus described in 711, 691, JP-A-2002-123939, etc., and International Publication No. If the device described in 719 is used, a card-like device is preferable.
  • a method for producing a recording medium includes mixing a holographic recording layer forming composition by mixing a holographic recording composition by heating at room temperature or, if necessary, under safelight. After being prepared and degassed to suppress polymerization inhibition at the time of holographic exposure, the holographic recording layer-forming composition at room temperature or, if necessary, heated, is applied to the first substrate, and then A recording medium can be manufactured by laminating the two base materials so that air bubbles do not enter so as to have a predetermined thickness of the recording layer, and finally sealing the end.
  • the first base material and the second base material are fixed to a mold under a safelight so as to have a predetermined gap, and the holographic recording composition heated at room temperature or heated as necessary does not allow bubbles to enter.
  • the recording medium can be manufactured by filling the space between the first base material and the second base material by injection molding or suctioning under reduced pressure so that air bubbles do not enter, and finally sealing the end.
  • under safelight refers to an operation in a state where the wavelength of light at which the photopolymerization initiator becomes active is cut.
  • the holographic recording layer forming composition may be applied to a second substrate instead of the first substrate described above, And the second base material. Further, when sealing the first base material, the holographic recording layer and the end of the second base material, the liquid base such as a moisture-curable adhesive capable of sealing is used.
  • the sealing material may be crosslinked and sealed, or may be sealed in advance using an end sealing material on a ring for ensuring a predetermined thickness of the holographic recording layer.
  • the holographic recording method of the present invention it is desired to perform recording after reacting a binder-forming compound with the holographic recording medium described above in detail before the holographic exposure to form a binder. Based on the information, information light and reference light are incident from the first base material side and holographic exposure is performed to activate the photopolymerization initiator, and the compound having an ethylenic unsaturated bond by the active species is holographically exposed. It is characterized by recording information on holographic recording media by diffusion polymerization in the recording layer.
  • a recording layer forming composition is prepared without a solvent for dilution.
  • a uniform film thickness is obtained or the composition is wound during preparation of the composition. It is difficult to remove air bubbles. Therefore, when the recording layer forming composition is prepared, fluidity is required at room temperature or in a heated state.
  • the recording layer forming composition is liquid at room temperature and has low viscosity, it is difficult to secure the flatness as a recording medium, or the ethylenically unsaturated bond after recording information by holographic exposure. It is not preferable because the polymer formed by the compound having a combination may be displaced in the recording layer. .
  • a binder is formed on the holographic recording medium containing the above-mentioned essential components by crosslinking the binder-forming compound before the holographic exposure.
  • the polymer formed by diffusion polymerization of the compound having the compound having a saturated bond can be prevented from moving in the holographic recording layer.
  • holographic exposure is performed based on the information to be recorded, and the photopolymerization initiator is activated.
  • Information can be recorded on a holographic recording medium by diffusing and polymerizing a compound having an unsaturated bond.
  • the crosslinking reaction for forming the above-mentioned binder in the present recording method may be performed by crosslinking all combinations of functional groups that can be reacted, or by crosslinking only a part of the combination within a range that does not cause a practical problem. good.
  • the ethylenic acid remaining in the recording layer may be exposed to light and heat, if necessary, for the purpose of fixing the recorded holographic information. It is preferable that the compound having an unsaturated bond is photopolymerized with a photopolymerization initiator, and that the uncrosslinked functional groups of the remaining binder-forming compound are thermally crosslinked.
  • the light used for exposure is exposed to the entire recording medium at a time.
  • the light may be applied before, at the same time as, or after the simultaneous exposure, or a plurality of heat treatments may be performed. They may be combined.
  • an information light and a reference light are made to enter the holographic recording medium described above in detail from the first base material side based on the information to be recorded.
  • Exposure to activate the photopolymerization initiator record the information on the holographic recording medium by diffusing and polymerizing the compound having an ethylenically unsaturated bond with this active species, and record the information on the holographic recording medium
  • the recorded information is stabilized by further performing heat and light irradiation on the entire holographic recording medium.
  • This embodiment differs from the first embodiment described above in that, when the recording layer forming composition is prepared, the composition, which flows in a heated state but does not flow at room temperature, has a shear stress.
  • This is an effective recording method for a holographic recording medium in which a recording layer is formed by a recording layer forming composition having a gelling or thixotropy at room temperature unless added. In such a recording medium, there is practically no problem in securing the flatness of the recording medium and preventing the movement of the polymer formed by diffusion polymerization of the compound having an ethylenically unsaturated bond.
  • the compound having an ethylenically unsaturated bond remaining in the recording layer by light and heat for the purpose of further improving the preservability of recorded information
  • the light used for exposure is exposed to the entire recording medium at a time, as in the first embodiment described above. It may be a deviation or a combination of several heat treatments.
  • any apparatus capable of recording / reproducing on the recording medium of the present invention can be used.
  • a recording and reproducing apparatus include, for example, U.S. Patent Nos. 5,719,691, 5,838,467, 6,163,391, 6,414, No. 296, U.S. Publication No. 2002-136143, JP-A-9-305978, JP-A-10-124872, JP-A-11-21 9540, JP-A-2000-98862, JP-A-2000-298837, JP-A-2001-23 No. 169, 2002-83431, 2002-123949, 2002-123948, 2003-43904, WO 99/57719, 02Z05270, 02Z75727, etc. Can be done.
  • the photopolymerization initiator in the recording medium was activated to enable holographic recording, and that the recording was performed.
  • Any laser light source that can read holograms can be used without particular limitation. Examples of such light sources are a semiconductor laser in the blue-violet region, an argon laser, a He—Cd laser, a frequency doubled YAG laser, He—Ne lasers, Kr lasers, semiconductor lasers in the near infrared region, and the like can be given.
  • holographic recording media before recording and holographic recording media with little recorded information and with the possibility of additional recording when the wavelength of the light source normally used for holographic recording is assumed to be I nm, ( ⁇ +
  • recording is performed by exposing the recording medium to laser light by exposing the recording medium to a case or cassette that can at least block light of 100 nm or less, preferably ( ⁇ + 200) nm or less. Only information is recorded by taking out the case ⁇ from the cassette and irradiating it with a laser beam under light shielding.
  • the recording medium on which information is recorded by the holographic recording method of the present invention can be taken out of a light-shielding case or cassette such as the above-mentioned light-shielding case, and can be handled in a light room like a CD or DVD. Can be used as information media.
  • a holographic information recording layer is sandwiched between a first base material and a second base material, and the holographic information recording layer has a compound having an isocyanate group and a compound having a hydroxyl group, A compound having an isocyanate group and a compound having an amino group, a compound having a carbodiimide group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a compound having a mercaptan group Compounds, compounds having a vinyl group and a compound having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxolane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, ratatone, Cyclic orthoester, ring Condition A region mainly composed of
  • the refractive index is 1.55 or more.
  • the refractive index of a region mainly containing a binder is higher than that of a region mainly containing a radical polymer formed by radical polymerization containing at least a compound having an ethylenically unsaturated bond as a monomer unit.
  • Information is recorded by lowering the refractive index of the region mainly containing the binder than the refractive index of the region mainly containing the radical polymer.
  • the information recording layer on which information is recorded under normal handling conditions is unlikely to change, so that there is almost no deterioration in readout by the reproducing apparatus over time.
  • the binder-forming compound (A-1-1-3) used in preparing the holographic recording layer-forming composition the compound having an ethylenically unsaturated bond (B-1-1-10), 'The combination initiator (C-115) and the dye (D-1-1-3) are shown below.
  • A-4) Urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.)
  • A-5) Polypropylene glycol diglycidyl ether (Epolite 200P, manufactured by Kyoeisha Chemical Co., Ltd.)
  • Solution 1 was prepared by mixing 48.92 g of the binder-forming compound (A-5 above) and 8.74 g of the binder-forming compound (A-7 above) under safelight.
  • B-5 a compound having an ethylenically unsaturated bond
  • the composition finally prepared was deaerated with nitrogen, and the gas components contained in the ultrasonic cleaning device were removed. Was removed, and a holographic recording layer forming composition 1 for comparison was prepared.
  • holographic recording layer forming composition 1 In the holographic recording layer forming composition 1 described above, the compound having an ethylenically unsaturated bond and the photopolymerization initiator were changed to the compounds and addition amounts shown in Table 1, and further added to the solution 1 as shown in Table 1.
  • Holographic recording layer forming composition 2-9 was prepared in the same manner as holographic recording layer forming composition 1 except that the amount of sensitizing dye was dissolved. ⁇ table 1
  • binder-forming compound (A-3 above) was added to 36.
  • Omg of 2,6-di (t-butyl) —4-methylphenol and 67. lmg of urethane curing catalyst (previous Solution A-4) was mixed and dissolved to prepare solution 2.
  • 7.92 g of a binder-forming compound (A-1), 23.75 g of a binder-forming compound (A-2) 8.00 g of a compound having an ethylenically unsaturated bond (see above) B-1) and 2.00 g of a compound having an ethylenically unsaturated bond (B-4) are mixed and dissolved to prepare a solution B.
  • a holographic recording layer-forming composition 1 124 was prepared in the same manner as the holographic recording layer-forming composition 10 except that the sensitizing dye in the amount described in Table 2 was dissolved in Solution 2. .
  • a binder-forming compound (A-8.90 g of a compound having an ethylenically unsaturated bond (B_l 1.00 g of a compound having an ethylenically unsaturated bond) (Solution B-0.93 g of photoinitiator (C-2 above) and 9.6 mg of sensitizing dye (D-3) were mixed and dissolved to prepare solution C.
  • a mouth graphic recording layer forming composition 26-30 was prepared in the same manner as the recording layer forming composition 25.
  • a compound having an ethylenically unsaturated bond was dissolved in the isocyanate compound shown in Table 4, and then a photopolymerization initiator was dissolved in this solution.
  • a solution in which a sensitizing dye and a urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) are dissolved in a compound having two or more hydroxyl groups in the molecule is dissolved in the photopolymerization initiator.
  • Holographic recording composition 31 1-46 was prepared by adding nitrogen to the solution and deaeration of the last prepared composition with nitrogen, and then removing the contained gas components by vacuum degassing. . [Table 4]
  • first substrate and a second substrate one side of 0.5 mm (dl, d2) glass is made to have a reflectance of 0.1% with incident light perpendicular to the wavelength of 532 nm.
  • Anti-reflection treatment was applied.
  • a polyethylene terephthalate sheet was used as a spacer so that the recording layer thickness (Dh) shown in Table 4 was obtained on the surface of the first base material which had not been subjected to the antireflection treatment.
  • Attach the graphic recording composition to the first substrate, and in the next V do not wrap the air layer over the holographic recording composition on the non-reflective surface of the second 'substrate.
  • the first base material and the second base material were bonded via a spacer.
  • the ends were sealed with a moisture-hardening adhesive, and heat-treated under the heat treatment conditions described in Table 5 to produce a holographic recording medium.
  • One side of 0.5 mm (d 1) thick glass, perpendicular to 532 nm wavelength By subjecting the first substrate to anti-reflection treatment so that the reflectance by light becomes 0.1%, one side of the glass with a thickness of 5 mm (d 2) is exposed to a wavelength of 532 nm.
  • the second substrates were each produced by performing aluminum vapor deposition so that the reflectance by vertical incident light became 90%.
  • a polyethylene terephthalate sheet was formed into a spacer so that the recording layer had a thickness (D h) shown in Table 5 on the surface of the first base material which had not been subjected to the anti-reflection treatment.
  • the described holographic recording layer forming composition is applied to the first base material, and then the aluminum-deposited surface of the second base material is bonded onto the holographic recording composition so that an air layer is not wound.
  • the first base material and the second base material were bonded via a spacer. Finally, the end was sealed with a moisture-curable adhesive, and heat-treated under the heat treatment conditions shown in Table 6 to produce a holographic recording medium.
  • a digital pattern is displayed on a holographic recording medium equipped with an Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight.
  • Holograms were obtained by holographic exposure of this digitally patterned with an energy of cm 2 .
  • the generated reproduction light was read by a CCD, and the minimum exposure amount at which a good digital pattern was reproduced was measured as the sensitivity (S11).
  • the holographic recording media stored at 50 for 1 week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S12).
  • the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
  • a digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight.
  • a hologram was obtained by holographic exposure with this digital patterned at an energy of j / cm 2 .
  • the holographic recording medium was treated under a 70,000 lux sunshine fader for 5 minutes, and then heated at 100 ° C. for 5 minutes.
  • the Nd: YAG laser (532 nm) as a reference beam under safe light
  • the processed recording medium is read using a CCD to read the generated reproduction light, and the minimum exposure amount at which a good digital pattern can be reproduced is determined by the sensitivity ( S 21).
  • the holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S22).
  • the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
  • the holographic recording medium produced as described above was not stored for 1 week at 50 ° C under shading, and a series of multiple holograms were written.
  • the sensitivity (recording energy) was measured and evaluated according to the following method, and the results obtained are shown in Table 9.
  • a digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight.
  • a hologram was obtained by performing holographic exposure with this digital pattern at an energy of jZcm 2 .
  • the holographic recording medium was treated under a 70,000 lux sunshine dome for 5 minutes, and then heated at 100 ° C for 5 minutes.
  • the Nd: YAG laser (532 nm) as a reference beam under safe light
  • the processed reproduction medium was read by a CCD and the minimum exposure required to reproduce a good digital photo pattern was obtained.
  • the light intensity was measured as sensitivity (S31).
  • the holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S32).
  • the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
  • the digital pattern was displayed on a holographic recording medium that had not been stored at 50 ° C for 1 week under a safelight using a holographic manufacturing apparatus equipped with a blue-violet semiconductor laser (405 nm) ⁇ . Hologram by this digitally patterned holographic exposure with energy of Om j / cm 2 Got. Next, the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes. The processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD. Was measured as the sensitivity (S41). The holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S42).
  • the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
  • the holographic recording medium prepared as described above was not stored for 1 week at 50 ° C under shading, and the holographic recording medium was not stored according to the procedure described in Japanese Patent Application Laid-Open No. 2002-123939. Then, a series of multiple holograms were written, and the sensitivity (recording energy) was measured and evaluated according to the following method. The obtained results are shown in 11.
  • Holographic recording with a blue-violet semiconductor laser (405 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight A digital pattern was displayed on the apparatus, and a hologram was obtained by performing holographic exposure with the digital pattern at an energy of 0.1 to 30 mj / cm 2 .
  • the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes.
  • the processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD.
  • the holographic recording medium stored at 50 ° C. for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S52).
  • the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
  • the holographic information media prepared in Table 8, Table 9, Table 10 and Table 11 in which the recorded information is fixed are stored under the following conditions, and before and after storage, digital data is created by a method suitable for each information medium.
  • the patterns were reproduced and evaluated, and the difference between the minimum exposure light amount before and after storage at which a good digital pattern was reproduced was evaluated by the following method. The obtained results are shown in Table 12.
  • the holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
  • ASh Minimum exposure sensitivity difference (S2h)-Minimum exposure sensitivity before storage (S1h)
  • the samples were stored at a temperature of 35 ° C under a sunshine fadeometer of 70,000 lux for 1 week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
  • ASw Minimum exposure sensitivity difference
  • S2w Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
  • the holographic information medium of the present invention shows good results without a decrease in sensitivity for reproduction.
  • the holographic recording medium produced as described above is written with a series of multiplexed holograms according to the procedure described in US Pat. No. 5,719,691, and the sensitivity (recording energy), The contraction resistance and the contrast of the refractive index were measured and evaluated, and the obtained results are shown in Table 13.
  • the holographic recording media was treated under a sunshine feed meter of 70,000 lux for 5 minutes and then heated at 100 ° C. for 5 minutes.
  • Nd: YAG laser (532 nm) as a reference beam
  • the read-out light generated is read by a CCD under safe light and the minimum exposure amount at which a good digital pattern can be reproduced is determined. (S1) was measured.
  • the shrinkage resistance is indicated by a shrinkage rate measured by the following method.
  • FIG. 1 is a schematic diagram showing the principle of a measuring device for measuring a shrinkage ratio. That is, the emission point of the white illumination light source that illuminates the holo-drama 3 is 01, and the viewpoint of the observer is 02.
  • a white illumination light source 4 is installed at a light emitting point 01
  • a spectroscope 5 is installed at a viewpoint 02.
  • the spectrometer 5 is connected to a bass computer 6, and a moving pinhole plate 7 having a pinhole 8 through which only a part of light is transmitted is provided on the upper surface of the hologram 3 for measuring the luminance distribution of the spectral wavelength. Is installed.
  • the movable pinhole plate 7 is configured to be attached to an XY stage (not shown) and move to an arbitrary position.
  • the moving pinhole plate 7 Measure e c , ei, at each position of hologram 3 while moving.
  • the hologram shrinkage at point P (1, J) is M (1, J)
  • the hologram shrinkage M (1, J) is the average refractive index of the optical image recording material before recording.
  • nr is the average refractive index of the hologram after the development processing is nc, it can be expressed by the following equation.
  • ⁇ o is the incident angle on the holographic recording medium
  • er is the incident angle of the reference light on the holographic recording medium.
  • the contrast of the refractive index was determined from the diffraction efficiency measured according to the following method.
  • the diffraction efficiency was measured using an ART25C type spectrophotometer manufactured by JASCO Corporation. A photomultimeter with a 3 mm wide slit was placed on a 20 cm radius circle centered on the sample. It was installed in. Monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio of the largest value other than the specularly reflected light to the value when directly incident light is received without placing the sample is defined as the diffraction efficiency, and the refractive index contrast ( ⁇ ) is calculated from the diffraction efficiency of the obtained hologram.
  • the refractive index contrast ( ⁇ ) is calculated from the diffraction efficiency of the obtained hologram.
  • the recording medium of the present invention has high sensitivity, low shrinkage ratio, and high contrast as compared with the comparative example, and shows good results.
  • the hologram was obtained by performing a quick exposure.
  • the holographic recording media was treated under a sunshine feedmeter of 70,000 lux for 5 minutes and then heat-treated at 100 ° C. for 5 minutes.
  • Nd: YAG laser (532 nm) as a reference beam under safe light
  • this processed recording medium was read using a CCD to read out the generated reproduction light, and the minimum exposure amount at which a good digital pattern could be reproduced was measured as the sensitivity (S 1).
  • the holographic information media created in Tables 13 and 14 in which the recorded information is fixed are stored under the following conditions, and before and after the storage, the digital pattern is reproduced and evaluated by a method suitable for each information medium.
  • the difference between before and after the storage of the minimum exposure amount at which a good digital pattern was reproduced was evaluated by the following method, and the obtained results are shown in Table 15.
  • the degree of coloring of the holographic information media was evaluated by the following method, and the obtained results are shown in Table 16. Knit preservation)
  • the holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
  • Minimum exposure sensitivity difference ( ⁇ Sh) Minimum exposure sensitivity after storage (S2h)-Minimum exposure sensitivity before storage (S1h)
  • the samples were stored at a temperature of 35 ° C under a 70,000 lux sunshine fade meter for one week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
  • ASw Minimum exposure sensitivity difference
  • S2w Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
  • the holographic information medium of the present invention shows good storage stability without lowering the sensitivity for reproduction as compared with the comparative example.
  • a holographic information media was prepared by heating for a while. Then, it was stored under the following conditions, and before and after storage, the transmittance of each information medium was measured by Hitachi Spectrophotometer U-4100, manufactured by Hitachi High-Techno-Gee Corporation, and evaluated by the following method.
  • the holographic information media was stored at 80 ° C for 2 weeks, and the transmittance difference ( ⁇ ) of 400 nm before and after storage was determined.
  • Transmittance difference Transmittance before storage (Tl h)-Transmittance after storage (T2h) (Light storage stability)
  • Transmittance difference (ATw) Transmittance before storage (Tlw)-Transmittance after storage (T2w)
  • the holographic information medium of the present invention is less colored and shows better storage stability than the comparative example.
  • a holographic recording medium having high sensitivity and excellent preservability, a holographic recording method, and a holographic information medium recorded with holographic recording are obtained.

Abstract

A holographic recording medium wherein a holographic recording layer is interposed between a first base and a second base is characterized in that the holographic recording layer contains at least a binder-forming compound, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator which is capable of initiating polymerization reaction of the compound having an ethylenically unsaturated bond, in that the content of the compound having an ethylenically unsaturated bond is within 1-50 mass% relative to the total amount of the composition, and in that the photopolymerization initiator contains a compound represented by the following general formula (1). [A-Fe-B]+·X- (1) By having such a structure, the holographic recording medium can be highly sensitive and excellent in storage stability. Also disclosed are a holographic recording method and a holographically recorded holographic information media.

Description

ホログラフィック記録メディア、 ホログラフィック記録方法  Holographic recording media, holographic recording method
およびホログラフィック情報メディア 技術分野  And holographic information media
本発明は、 大容量化、 高速転送が可能なホログラフィック記録メディアに関し、 さらにホログラフィック記録方法および情報が記録されたホログラフィック情報 ：関する。 背景技術  The present invention relates to a holographic recording medium capable of large-capacity and high-speed transfer, and further relates to a holographic recording method and holographic information on which information is recorded. Background art
近年、インターネットの普及やブロードパンド化による高速大容量のデータのや り取りが増加しており、また各国政府の推進による電子政府の拡張により、各所属 機関に保管されるデータの容量が急速に拡大してきている。 さらに、テレビジョン 放送におけるハイビジョンの普及や地上波デジタルの普及などにより今後高記憶 容量の記録メディアが必要となると予想され、 その中で、 B l u- r a yディスク や H D D VDディスク等の次世代の光記録メディアが今後普及していくと思わ れる。 しかしながら、次々世代の記録メディアについては、種々の方式が提案され ているが今だ本命不在な状態に有る。  In recent years, the exchange of high-speed, large-volume data has increased due to the spread of the Internet and the spread of broadband networks, and the expansion of e-government promoted by governments of various countries has led to a rapid increase in the amount of data stored at each institution. It is expanding. Furthermore, with the spread of high-definition television and the spread of terrestrial digital broadcasting, it is expected that high-capacity recording media will be required in the future. Among them, the next generation of Blu-ray discs, HDD VD discs, etc. Optical recording media is expected to spread in the future. However, for the next-generation recording media, various methods have been proposed, but they are still absent.
この次々世代の記録メディアの中で、ページ方式のメモリシステム、特にホログ ラフィック記録が、従来のメモリ装置に代わるものとして提案され、高記憶容量で かつランダムァクセスが可能な高速転送可能な方式であることから近年注目を集 めている。 このホログラフィック記録については幾つかの総説（例えば、 H a n s J . C o u f a 1等著 「H o l o g r a p h i c D a t a S t o r a g e (S p r i n g e r S e r i e s i n Op t i c a l S c i e n c e s, Vo l 76)」（S p r i n g e r—V e r 1 a g GmbH & Co. KG、 2000年 08月）） 等に詳細が説明されている。 Among the next-generation recording media, a page-type memory system, especially holographic recording, has been proposed as an alternative to the conventional memory device, and has a high storage capacity and a high-speed transfer method capable of random access. For some reason, it has been drawing attention in recent years. Some reviews of this holographic record (eg, Hans J. Coufa 1 et al., Holographic Data at Storage (Springers Seriesin Optical Sciences, Vol 76) (Springer-Ver 1 ag GmbH & Co. KG, August 2000), etc. Is described in detail.
このホログラフィック記録における記録方式としては、例えばホログラフィック 記録層の両側に透明な基材が配置されたホログラフィック記録メディアを用いた 記録方法 （例えば、 米国特許 5， 719, 691号明細書） や、 ホログラフィック 記録層の片面側に配置された反射面とを備えたホログラフィック記録メディアを 用いた記録方法 （例えば、 特開 2002-123949号公報） などが提案されて いる。  As a recording method in this holographic recording, for example, a recording method using a holographic recording medium in which transparent substrates are arranged on both sides of a holographic recording layer (for example, US Pat. No. 5,719,691) and A recording method using a holographic recording medium having a reflective surface disposed on one side of a holographic recording layer (for example, JP-A-2002-123949) and the like have been proposed.
このようなホログラフィック記録メディアは、ホログラフィック露光することに より該メディア内のホログラフィック記録層内の屈折率を変化させることにより 情報を記録し、この記録されたメディァ内の屈折率の変化を読み取ることにより情 報を再生させることを基本原理にしており、このホログラフィック記録層としては 無機材料を利用した材料 （例えば、 英国特許 9， 929, 953号明細書)、 光で 構造異性ィ匕する化合物を利用した材料 (例えば、特開平 10-340479号公報)、 あるいはフォトポリマーの拡散重合を利用した材料 (例えば、米国特許 4， 942, 1 12号明細書） など種々提案されている。 これらの中で、特許文献 5で記載され ているフォトポリマーを使用した材料においては記録層形成組成物を作製する際 に揮発性溶剤を使用をするため、記録層の厚さは最大 150 μπι程度に制限されて いる。 さらに、重合によって引き起こされる 4一 10%の体積収縮は、記録された 情報を再生する際の信頼性に悪影響を与えていた。  Such a holographic recording medium records information by changing a refractive index in a holographic recording layer in the medium by holographic exposure, and detects a change in a refractive index in the recorded medium. The basic principle is that information is reproduced by reading. The holographic recording layer is made of a material using an inorganic material (for example, UK Patent No. 9,929,953), and is structured by light. (For example, Japanese Patent Application Laid-Open No. H10-340479) or a material using diffusion polymerization of a photopolymer (for example, US Pat. No. 4,942,112). Among these, the material using the photopolymer described in Patent Document 5 uses a volatile solvent when producing the recording layer forming composition, so that the thickness of the recording layer is at most about 150 μπι. Is restricted to In addition, the volume shrinkage of 4-10% caused by polymerization adversely affected the reliability of reproducing the recorded information.
上述した欠点を改善するために、無溶剤で比較的体制収縮の少ないカチオン重合 を利用したホログラフィック記録層形成組成物 （例えば、米国特許 5 , 7 5 9 , 7 2 1号明細書） などが提案されている。 し力 しながら、 この記録層形成組成物にお いては光力チオン重合を起こすモノマー以外が液状物質であるため、ホログラフィ ック露光により記録層内のモノマーが光重合して形成された島状部分が移動して しまう恐れが有ったり、装置内の環境温度の変化により液状物質の体積が膨張する などの欠点を有していた。 In order to improve the above-mentioned drawbacks, cationic polymerization with no solvent and relatively small system shrinkage And a holographic recording layer forming composition utilizing the same (for example, U.S. Pat. No. 5,759,721). However, since the recording layer-forming composition is a liquid substance other than the monomer that causes photo-induced thione polymerization, the island-shaped monomer formed by photo-polymerization of the monomer in the recording layer by holographic exposure is used. There are drawbacks such as the possibility that the part may move, and the volume of the liquid substance expands due to changes in the environmental temperature inside the device.
このような欠点を改善するためにホログラフィック露光での記録にはラジカル 重合を用い、この露光前のラジカル重合可能なモノマーを保持する為にバインダー をメディア形成後に形成させる糸且成物 （例えば、米国特許 6 , 1 0 3， 4 5 4号明 細書)'などが提案されており、 このような組成物を用いることによってホログラフ イツク記録層の膜厚を厚くでき、かつ体積収縮を少なくすることができるが今だ十 分であるとは言えない。  In order to remedy such defects, radical polymerization is used for recording in holographic exposure, and a binder is formed after the formation of the medium in order to retain the radically polymerizable monomer before the exposure (for example, a thread-forming material (for example, U.S. Pat. No. 6,103,454) has been proposed. Use of such a composition can increase the thickness of the holographic recording layer and reduce volume shrinkage. Can be done, but it is still not enough.
一方、ホログラフィック記録メディアにホログラフィッ-ク記録を行う場合、低ェ ネルギ一で露光できることが記録速度を向上させる為には必須となる。この記録速 度、言い換えれば記録感度を向上させるためには、使用される拡散重合させる為の モノマー、バインダ一形成化合物、増感色素おょぴラジカル開始剤の選択および組 み合わせが重要となる。例えばパインダ一形成化合物ではなく予め高重合度のバイ ンダーを用いたホログラム記録用感光性組成物（例えば、国際公開第◦ 3 Z 0 8 1 On the other hand, when performing holographic recording on a holographic recording medium, it is essential to be able to expose with low energy in order to improve the recording speed. In order to improve the recording speed, in other words, the recording sensitivity, it is important to select and combine monomers, binder-forming compounds, sensitizing dyes and radical initiators for use in diffusion polymerization. . For example, a hologram recording photosensitive composition using a binder having a high degree of polymerization in advance instead of a binder-forming compound (for example, International Publication No. 3Z081)
3 4 4号パンフレツト）が提案されているが、バインダーとしてポリマーを使用し ている為ホロダラム記録用感光性組成物を調製する際に溶剤を必要とし、記録層の 厚さが十分稼げない等の欠点を有していた。 発明の開示 本発明は、 上記の課題を鑑みてなされたものであり、本発明の目的は、感度が高 く保存性に優れたホログラフィック記録メディア、ホログラフィック記録方法およ びホログラフィック記録されたホログラフィック情報メディアを提供することに める。 No. 34 4 pamphlet) has been proposed. However, since a polymer is used as a binder, a solvent is required when preparing a photosensitive composition for horodharam recording, and the thickness of the recording layer cannot be sufficiently increased. Had disadvantages. Disclosure of the invention The present invention has been made in view of the above problems, and an object of the present invention is to provide a holographic recording medium, a holographic recording method, a holographic recording method, and a holographic recorded holographic recording medium having high sensitivity and excellent storage stability. Decide to provide information media.
上記目的を達成するため、 本発明の一実施例は、 （1 ) 第一基材と第二基材の間 に、バインダー形成化合物、エチレン性不飽和結合を有する化合物、前記エチレン 性不飽和結合を有する化合物の重合反応を開始することのできる光重合開始剤、お よび、光重合開始剤を分光増感することができる増感色素を含有するホログラフィ ック記録層を有するホログラフィック記録メディアにおいて、  To achieve the above object, one embodiment of the present invention provides: (1) a binder-forming compound, a compound having an ethylenically unsaturated bond between the first base material and the second base material, A holographic recording medium having a holographic recording layer containing a photopolymerization initiator capable of initiating a polymerization reaction of a compound having the formula (I) and a sensitizing dye capable of spectrally sensitizing the photopolymerization initiator. ,
前記パインダー形成化合物が以下の （1 )〜（8 ) から少なくとも 1つ選ばれる化 合物の組み合わせを含み、 Wherein the binder-forming compound comprises a combination of at least one compound selected from the following (1) to (8):
( 1 ) ィソシァネート基を有する化合物と水酸基を有する化合物、  (1) a compound having an isocyanate group and a compound having a hydroxyl group,
( 2 ) イソシァネート基を有する化合物とァミノ基を有する化合物、  (2) a compound having an isocyanate group and a compound having an amino group,
( 3 ) カルポジイミド基とカルボキシル基を有する化合物、  (3) a compound having a carbodiimide group and a carboxyl group,
( 4 ) 不飽和エステル基を有する化合物とアミノ基を有する化合物、  (4) a compound having an unsaturated ester group and a compound having an amino group,
( 5 ) .不飽和エステル基を有する化合物とメルカプタン基を有する化合物、 (5) a compound having an unsaturated ester group and a compound having a mercaptan group,
( 6 ) ビュル基を有する化合物とシリコンヒ ドリ ド基を有する化合物、 (6) a compound having a bull group and a compound having a silicon hydride group,
( 7 ) ォキシラン基を有する化合物とメルカブタン基を有する化合物、  (7) a compound having an oxysilane group and a compound having a mercaptan group,
( 8 ) ォキシラン、 ォキセタン、 テトラヒ ドロフラン、 ォキセパン、 単環ァセター ル、 双環ァセタール、 ラタトン、 環状オルトエステル、 および環状カーボナートか ら選ばれた基を分子中に 1個以上有する化合物と熱カチオン重合開始剤、  (8) Initiation of thermal cationic polymerization with a compound having at least one group selected from oxysilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, rataton, cyclic orthoester, and cyclic carbonate in the molecule Agent,
前記エチレン性不飽和結合を有する化合物の含有量が組成物全体に対して 1一 The content of the compound having an ethylenically unsaturated bond is 11 to the entire composition.
5 0質量％の範囲であり、 前記光重合開始剤が少なくとも下記一般式（1)で表される化合物を含有するこ とを特徴とするホログラフィック記録メディアである。 In the range of 50% by mass, A holographic recording medium, wherein the photopolymerization initiator contains at least a compound represented by the following general formula (1).
一般式 (1) [A-F e-B] + · X- General formula (1) [A-F e-B] + · X-
(式中 Aは、無置換またはアルキル基置換シクロペンタジェ-ル基、 Bは無置換ま た置換アレーン基、 X—はフッ素原子を含有する対ァニオンを表す。） (In the formula, A represents an unsubstituted or alkyl-substituted cyclopentagel group, B represents an unsubstituted or substituted arene group, and X— represents a fluorine atom-containing anion.)
(2) 本発明においては、 前記バインダー形成化合物が、 前記 （1) イソシァネー ト基を有する化合物と水酸基を有する化合物、 または前記 (7) ォキシラン基を有 する化合物とメルカブタン基を有する化合物を含むことを特徴とする前記 (1)記 載のホログラフィック記録メディアである。  (2) In the present invention, the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, or (7) a compound having an oxysilane group and a compound having a mercaptan group. The holographic recording medium according to the above (1), characterized by the following.
(3) 本発明においては、 前記バインダー形成化合物が、 前記 (1) イソシァネー ト基を有する化合物と水酸基を有する化合物を含み、且つ前記イソシァネート基を 有する化合物は 3個以上のイソシァネート基を化合物中 3 0質量％以上 6 5質 量。 /0以下となるように含有することを特徴とする前記（1)記載のホログラフィッ ク記録メディアである。 (3) In the present invention, the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, and the compound having an isocyanate group has three or more isocyanate groups in the compound. 0 mass% or more 65 mass. The holographic recording medium according to the above (1), wherein the holographic recording medium is contained so as to be / 0 or less.
(4)本発明においては、イソシァネート基を有する化合物全体に対して、 3個以 上のイソシァネート基を化合物中 30質量％以上 6 5質量％以下となるように含 有する前記イソシァネート基を有する化合物が、 5— 1 00質量％以下含有してい ることを特徴とする前記 (3) に記載のホログラフィック記録メディアである。  (4) In the present invention, the compound having an isocyanate group containing at least 3 isocyanate groups in an amount of 30% by mass or more and 65% by mass or less based on the entire compound having the isocyanate group is used. The holographic recording medium according to (3), wherein the holographic recording medium contains 5 to 100% by mass or less.
(5) 本発明においては、前記イソシァネート基を有する化合物の分子量が、 20 0以上 500以下であることを特徴とする前記（3) のホログラフィック記録メデ ィァである。  (5) In the present invention, the holographic recording medium according to (3), wherein the compound having an isocyanate group has a molecular weight of 200 to 500.
(6) 本発明においては、前記水酸基を有する化合物が、分子量 1 00以上 200 0以下の分子内に 2個以上の水酸基を有する化合物であることを特徴とする前記 (3) に記載のホログラフィック記録メディアである。 (6) In the present invention, the compound having a hydroxyl group is a compound having two or more hydroxyl groups in a molecule having a molecular weight of 100 to 2,000. A holographic recording medium according to (3).
(7)本発明においては、前記エチレン性不飽和結合を有する化合物として、分子 内に （メタ） ァクリロイル基を有する化合物を含んでいることを特徴とする前記 (7) In the present invention, the compound having an ethylenically unsaturated bond includes a compound having a (meth) acryloyl group in a molecule.
(1) 記載のホログラフィック記録メディアである。 The holographic recording medium described in (1).
(8)本発明においては、前記エチレン性不飽和結合を有する化合物として、屈折 率が少なくとも 1. 5 5以上の化合物を前記エチレン性不飽和結合を有する化合物 全体に対して 5 0質量。 /0以上 1 0,0質量％以下含有することを特徴とする前記(8) In the present invention, as the compound having an ethylenically unsaturated bond, a compound having a refractive index of at least 1.55 or more is 50% by mass based on the whole compound having an ethylenically unsaturated bond. / 0 to 10.0% by mass.
(I) に記載のホログラフィック記録メディアである。 A holographic recording medium according to (I).
(9)本発明においては、前記ホログラフィック記録メディアの、前記第一基材の 厚みを D 1、前記第二基材の厚みを D 2、およぴ前記ホログラフィック記録層の厚 みを Dhとし、前記ホログラフィック記録層の厚み Dhが 200 μπι以上 2. 0 m m以下、 0. 1 5 Dh/ (D 1 +D 2) ≤ 2. 0、 かつ D 1≤ D 2の関係を満た すことを特徴とする前記 （1) に記載のホログラフィック記録メ^ ^ィァである。  (9) In the present invention, in the holographic recording medium, the thickness of the first base material is D1, the thickness of the second base material is D2, and the thickness of the holographic recording layer is Dh. The thickness Dh of the holographic recording layer is 200 μπι or more and 2.0 mm or less, 0.15 Dh / (D 1 + D 2) ≤ 2.0, and the relationship of D 1 ≤ D 2 is satisfied. The holographic recording medium according to the above (1), characterized in that:
(1 0)本発明においては、前記第一基材が透明であり、前記第一基材においてホ ログラフィック記録層に接する面とは反対の面に反射防止処理がなされているこ とを特徴とする前記 (1) に記載のホログラフィック記録メディアである。  (10) In the present invention, the first base material is transparent, and an antireflection treatment is performed on a surface of the first base material opposite to a surface in contact with the holographic recording layer. The holographic recording medium according to the above (1).
(I I)本発明においては、前記第一基材の材質がガラスであることを特徴とする 前記 （1) に記載のホログラフィック記録メディアである。  (II) In the present invention, the holographic recording medium according to the above (1), wherein the material of the first base material is glass.
(1 2)本発明においては、前記第二基材に反射率が 70%以上の反射層が積層さ れていることを特徴とする前記 (1) に記載のホログラフィック記録メディアであ る。  (12) In the present invention, the holographic recording medium according to (1), wherein a reflective layer having a reflectance of 70% or more is laminated on the second base material.
(1 3)本発明においては、前記ホログラフィック記録メディアの形状がディスク 状またはカード状であることを特徴とする前記 (1) に記載のホログラフィック記 録メディアである。 (13) In the present invention, the holographic recording medium according to (1), wherein the holographic recording medium has a disk shape or a card shape. It is a recording media.
( 1 4 ) また、 本発明の一実施例は、 前記 （1 ) 記載のホログラフィック記録メデ ィァに記録する方法において、前記ホログラフィック記録メディアにホログラフィ ック露光する以前にバインダ一形成化合物を反応させパインダーを形成させた後 に、記録した!/、情報を基に第一基材側から情報光と参照光を入射させホログラフィ ック露光を行い、光重合開始剤を活性ィ匕させ、 この活性種によりエチレン性不飽和 結合を有する化合物をホログラフィック記録層内で拡散重合させることによりホ ログラフィック記録メディアに情報を記録することを特徴とするホログラフイツ ク記録方法である。  (14) In one embodiment of the present invention, in the method for recording on a holographic recording medium according to the above (1), the binder-forming compound is exposed before the holographic recording medium is subjected to holographic exposure. After the reaction and the formation of the binder, the recorded! /, Holographic exposure was performed by injecting information light and reference light from the first substrate side based on the information, and the photopolymerization initiator was activated. The holographic recording method is characterized in that information is recorded on a holographic recording medium by diffusion-polymerizing a compound having an ethylenically unsaturated bond with the active species in a holographic recording layer.
( 1 5 ) 本発明においては、 前記ホログラフィック記録方法において、 ホログラフ ィック記録メディアへの情報記録が終了した後に、さらにホログラフィック記録メ ディア全体に熱おょぴ光照射により安定ィヒさせることを特徴とする前記（1 4 )記 載のホログラフィック記録方法である。  (15) In the present invention, in the holographic recording method, after the information recording on the holographic recording medium is completed, the whole holographic recording medium may be further stabilized by irradiating heat. A holographic recording method as described in (14) above, which is characterized by the following.
( 1 6 ) また、 本発明の一実施例は、 前記 （1 ) 記載のホログラフィック記録メデ ィァに記録する方法において、前記ホログラフィック記録メディアに記録したい情 報を基に第一基材側から情報光と参照光を入射させホログラフィック露光を行い、 光重合開始剤を活性ィヒさせ、この活性種によりエチレン性不飽和結合を有する化合 物を拡散重合させることによりホログラフィック記録メディアに情報を記録し、ホ ログラフィック記録メディァへの情報記録が終了した後に、さらにホログラフイツ ク記録メディァ全体に熱および光照射を行うことにより記録された情報を安定ィ匕 させることを特徴とするホログラフィック記録方法である。  (16) In one embodiment of the present invention, in the method for recording on a holographic recording medium according to the above (1), the first base material side may be used based on information to be recorded on the holographic recording medium. The holographic exposure is performed by injecting information light and reference light from the holographic recording medium, the photopolymerization initiator is activated, and the compound having an ethylenically unsaturated bond is diffused and polymerized by the active species, whereby information is recorded on the holographic recording medium. And recording the information on the holographic recording medium, and irradiating the entire holographic recording medium with heat and light to stabilize the recorded information. It is a recording method.
( 1 7 ) また、 本発明の一実施例は、 前記 ( 1 ) に記載のホログラフィック記録メ ディアにおけるホログラフィック記録層に情報が記録されたホログラフィック情 報記録層が積層されたホログラフィック情報メディアにおいて、該ホログラフィッ ク情報記録層は、該パインダ一形成化合物から形成されたバインダーを主成分とす る領域と、エチレン性不飽和結合を有する化合物を少なくともモノマー単位として 含むラジカル重合させて形成したラジカル重合体を主成分とする領域とを有する ことを特徴とするホログラフィック情報メディアである。 図面の簡単な説明 (17) Further, an embodiment of the present invention provides a holographic information recording medium in which information is recorded on the holographic recording layer in the holographic recording medium according to (1). In a holographic information medium on which an information recording layer is laminated, the holographic information recording layer comprises a region mainly composed of a binder formed from the binder-forming compound and a compound having an ethylenically unsaturated bond. A holographic information medium having at least a region mainly composed of a radical polymer formed by radical polymerization containing as a monomer unit. Brief Description of Drawings
第 1図は、 収縮率の測定に用いる測定装置の原理を示す概略図である。 発明を実施するための最良の形態  FIG. 1 is a schematic diagram showing the principle of a measuring device used for measuring a shrinkage ratio. BEST MODE FOR CARRYING OUT THE INVENTION
以下、本努明のホログラフィック記録メディア、ホログラフィック記録方法およ びホログラフィック情報メディアについて詳述する。  Hereinafter, the holographic recording medium, the holographic recording method, and the holographic information medium of this effort will be described in detail.
本発明のホログラフィック記録メディアは、第一の基材と第二の基材の間にホロ グラフィック記録層が挟持されたホログラフィック記録メディアにおいて、該ホロ グラフィック記録層がィソシァネート基を有する化合物と水酸基を有する化合物、 ィソシァネート基を有する化合物とアミノ基を有する化合物、力ノレボジィミド基と カルボキシル基を有する化合物、不飽和エステル基を有する化合物とァミノ基を有 する化合物、 不飽和エステル基を有する化合物とメルカプタン基を有する化合物、 ビニル基を有する化合物とシリコンヒドリ ド基を有する化合物、ォキシラン基を有 する化合物とメルカブタン基を有する化合物、 並びに、 ォキシラン、 ォキセタン、 テトラヒドロフラン、 ォキセパン、 単環ァセターノレ、 双環ァセタール、 ラクトン、 環状オルトエステル、環状カーボナートから選ばれた基を分子中に 1個以上有する 化合物及び熱カチオン重合開始剤から選ばれる少なくとも一種のパインダ一形成 化合物、エチレン性不飽和結合を有する化合物、前記エチレン性不飽和結合を有す る化合物の重合反応を開始することのできる光重合開始剤を少なくとも含有し、前 記エチレン性不飽和結合を有する化合物の含有量が組成物全体に対して 1一 5 0 質量％の範囲であり、且つ前記エチレン性不飽和結合を有する化合物の重合反応を 開始することのできる光重合開始剤が少なくとも上記一般式（1 ) で表される化合 物を含有することを特徴としている。なお、ここで言うバインダ一形成化合物とは、 記録用組成物を調製時にはバインダーとしての重合体になっていない前駆体を指 し、このようなバインダー形成ィ匕合物を用いることにより後述で詳述するホロダラ フィック露光前後の記録メディアの収縮を防止することができるとともに、ホログ ラフィック記録メディアを作製する際の記録層の厚みを厚くすることができる。 本発明のパインダ一形成化合物は、ホログラフィック記録用組成物を調製した際 にはパインダ一形成化合物同士で重合あるいは架橋せず、後述するホログラフイツ ク記録メディアを作製時に、重合あるいは架橋させバインダーとする、 あるいはホ ログラフィック露光後に重合あるいは架橋させバインダーとすることを特徴とし ている。 このようにバインダ一形成化合物としては、例えばィソシァネート基を有 する化合物と水酸基を有する化合物、イソシァネート基を有する化合物とアミノ基 を有する化合物、カルポジイミド基とカルボキシル基を有する化合物、不飽和エス テル基を有する化合物とアミノ基を有する化合物、不飽和エステル基を有する化合 物とメルカブタン基を有する化合物、ビュル基を有する化合物とシリコンヒドリ ド 基を有する化合物、ォキシラン基を有する化合物とメルカプタン基を有する化合物、 並びに、 ォキシラン、 ォキセタン、 テトラヒ ドロフラン、 ォキセパン、 単環ァセタ ール、 双環ァセタール、 ラクトン、 環状オルトエステル、 環状カーボナートから選 ばれた基を分子中に 1個以上有する化合物及び熱カチオン重合開始剤から選ばれ る少なくとも 1種の組み合わせを適時選択して用いることができ、さらには前記選 択の中で温和な条件でバインダ一へと重合あるいは架橋させることができるイソ シァネート基を有する化合物と水酸基を有する化合物あるいはォキシラン基を有 する化合物とメルカブタン基を有する化合物から選ばれる少なくとも 1種がより 好ましい。 The holographic recording medium of the present invention is a holographic recording medium in which a holographic recording layer is sandwiched between a first base material and a second base material, wherein the holographic recording layer has a compound having an isocyanate group and a hydroxyl group. , A compound having an isocyanate group and a compound having an amino group, a compound having a phenolic group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a mercaptan Compounds having a group, compounds having a vinyl group and compounds having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxsilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetanol, and bicyclic acetal Lactone, cyclic orthoester, compound having at least one group selected from cyclic carbonate in the molecule and at least one kind of binder selected from thermal cationic polymerization initiators A compound having at least an ethylenically unsaturated bond, a compound having an ethylenically unsaturated bond, and a compound having at least a photopolymerization initiator capable of initiating a polymerization reaction of the compound having an ethylenically unsaturated bond. Is in the range of 150% by mass with respect to the whole composition, and the photopolymerization initiator capable of initiating the polymerization reaction of the compound having an ethylenically unsaturated bond is at least a compound represented by the general formula (I). It is characterized by containing the compound represented by 1). Here, the binder-forming compound refers to a precursor that is not a polymer as a binder when the recording composition is prepared, and will be described later in detail by using such a binder-forming compound. It is possible to prevent the recording medium from shrinking before and after the above-described holodographic exposure, and to increase the thickness of the recording layer when the holographic recording medium is manufactured. When the holographic recording composition is prepared, the binder-forming compound of the present invention does not polymerize or cross-link between the binder-forming compounds. Or by polymerizing or crosslinking after holographic exposure to form a binder. As described above, examples of the binder-forming compound include a compound having an isocyanate group and a compound having a hydroxyl group, a compound having an isocyanate group and a compound having an amino group, a compound having a carposimido group and a carboxyl group, and an unsaturated ester group. A compound having an amino group, a compound having an unsaturated ester group and a compound having a mercaptan group, a compound having a butyl group and a compound having a silicon hydride group, a compound having an oxysilane group and a compound having a mercaptan group, And compounds having at least one group selected from oxysilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, lactone, cyclic orthoester, and cyclic carbonate, and a thermal cationic polymerization initiator. Selection Re At least one combination may be used as appropriate, and further, a compound having an isocyanate group and a compound having a hydroxyl group, which can be polymerized or cross-linked to a binder under mild conditions in the above selection. Alternatively, at least one selected from a compound having an oxysilane group and a compound having a mercaptan group is more preferable.
本発明に用いられるイソシァネート基を有する化合物と水酸基を有する化合物 を架橋させる場合に用いられるィソシァネート基を有する化合物としては、とくに 制限は無く用いることができるが上述で詳述じた光重合成分であるエチレン性不 飽和結合を有する化合物をホログラフィック記録メディア作製後に十分に保持す る為には、 分子内に 2個以上のイソシァネート基を有する化合物がより好ましく、 後で詳述する本発明のホログラフィック記録メディアを作製する際に、常温で液状 或いは 1 0 0 °C以下の温度で液状の記録用組成物を二枚の基材間に所定の厚みで 挟持させることにより作製されるため、常温で液状或いは融点が 1 0 0 °C以下の化 合物がより好ましい。  The compound having an isocyanate group used for crosslinking the compound having an isocyanate group and the compound having a hydroxyl group used in the present invention can be used without any particular limitation, and is a photopolymerization component described in detail above. In order to sufficiently retain a compound having an ethylenically unsaturated bond after producing a holographic recording medium, a compound having two or more isocyanate groups in a molecule is more preferable. When a recording medium is produced, it is produced by sandwiching a recording composition that is liquid at room temperature or liquid at a temperature of 100 ° C. or less with a predetermined thickness between two substrates. A liquid or a compound having a melting point of 100 ° C. or less is more preferable.
このようなィ.ソシァネート基を有する化合物の具体的なものとしては、例えば 1， 8 -ジイソシァネート— 4一イソシァネートメチノレーオクタン、 2 -ィソシァネートェ チル— 2 , 6—ジイソシァネート力プロエート、 ベンゼン一 1， 3， 5—トリイソシァ ネート、 1—メチノレベンゼン—2 , 4 , 6—トリイソシァネート、 1， 3， 5—トリメ チルベンゼン - 2 , 4 , 6—トリイソシァネート、 ジフエニルメタン— 2， 4 , 4 ' 一 トリイソシァネート、 トリフエニルメタン一 4， A ' , 4 "—トリイソシァネート、 ビス （イソシアナートトリル） フエ二/レメタン、 ジメチレンジイソシァネート、 テ トラメチレンジイソシァネート、 へキサンメチレンジイソシァネート、 2， 2 -ジ メチ^/ペンタンジイソシァネート、 2， 2 , 4—トリメチノレペンタンジイソシァネ ート、 デカンジイソシァネート、 ω, ω' —ジイソシァネート— 1 , 3 -ジメチノレべ ンゼン、 ' ω， ω' -ジイソシァネート— 1， 2-ジメチルシクロへキサンジイソシァ ネート、 ω， ω—ジイソシァネート— 1 , 4—ジェチ /レベンゼン、 イソホロンジイソ シァネート、 1ーメチルシク口へキシノレ- 2， 4—ジィソシァネート、 ω, ω' -ジィ ソシァネート— 1 , 5 -ジメチルナフタレン、 ω, ω' —ジイソシァネート— η—プロ ピルビフエニル、 1， 3—フエ二レンジイソシァネート、 1—メチルベンゼン— 2, 4—ジィソシァネート、 1 , 3 -ジメチルべンゼン - 2 , 6—ジイソシァネート、 ナフ タレン— 1 , 4—ジイソシァネート、 1 , 1' —ジナフチノレ— 2， 2' —ジイソシァネ ート、 ビフエ二ルー 2， 4' -ジイソシァネート、 3, 3' —ジメチルビフエ二ル— 4， 4' —ジイソシァネート、 ジフエニルメタン—4, A' —ジイソシァネート、 2， 2' -ジメチルジフエニルメタン- 4， 4, ージィソシァネート、 ジシクロへキシル メタン一 4， 4' —ジイソシァネート、 3， 3' —ジメ トキシジフエニルメタン一 4， 4' —ジイソシァネート、 4, 4; -ジェトキシジフエニルメタン- 4， 4' —ジイソ シァネート、 トリレンジイソシァネート、 1， 5 -ナフチレンジイソシァネート、 キシリレンジィソシァネート、テトラメチレンキシリレンジィソシァネートなどが 挙げられ、さらに上記の各ィソシァネート化合物の 2量体又は 3量体のァダク ト体 (例えばへキサメチレンジィソシァネートの 2モノレのァダクト、へキサメチレンジ イソシァネート 3モルのァダクト、 2， 4一トリ レンジイソシァネート 2モノレのァ ダクト、 2， 4—トリレンジイソシァネート 3モルのァダクトなど）、 これらのイソ シァネートの中から選ばれる互いに異なる 2種以上のィソシァネート同志のァダ クト体、及びこれらのィソシァネートと 2価又は 3価のポリアルコール（例えばジ エチレングリコール、 ポリエチレングリコーノレ、 ジプロピレングリコーノレ、 ポリプ ロピレングリコール、 ポリテトラメチレングリコール、 トリメチロールプロパンな ど） とのァダクト体（例えばトリレンジィソシァネートとトリメチロールプロパン のァダクト、へキサメチレンジィソシァネートとトリメチロールプロパンのァダク トなど） などが挙げられる。 尚、 これらのイソシァネート化合物は、 1種単独でも 2種以上を組み合わせて用いても良い。 Specific examples of such a compound having a sosinate group include, for example, 1,8-diisocyanate-41-isocyanate methylenoloctane, 2-isocyanateethyl-2,6-diisocyanate, and benzene-1-one , 3,5-triisocyanate, 1-methinolebenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene -2,4,6-triisocyanate, diphenylmethane-2,4 , 4'-triisomethane, triphenylmethane-1,4'-triisocyanate, bis (isocyanatotolyl) phenyl / lemethane, dimethylene diisocyanate, tetramethylene diisocyanate , Hexanemethylene diisocyanate, 2,2-dimethy ^ / pentanediisocyanate, 2,2,4-trimethyolepentanediisocyanate Kane , Decane diisocyanate, ω, ω'-diisocyanate—1,3-dimethinolebenzene, 'ω, ω'-diisocyanate-1, 2-dimethylcyclohexanediisocyanate, ω, ω-diisocyanate-1, 4-diethylbenzene / isobenzene, isophorone diisocyanate, 1-methylcyclohexinole-2,4-diisocyanate, ω, ω'-di-socyanate-1,5-dimethylnaphthalene, ω, ω '-diisocyanate-η-propylbiphenyl, 1,3-phenylenediisocyanate, 1-methylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-2,6-diisocyanate, naphthalene-1,4-diisocyanate 1,1,1 '— Dinaphthinole 2,2'-diisocyanate, biphenyl 2,4'-diisocyanate, 3, 3'-dimethylbiphenyl 2,4 '—Diisocyanate, diphenylmethane-4, A' —Diisocyanate, 2,2'-dimethyldiphenylmethane-4,4, diisocyanate, dicyclohexylmethane 1,4,4 '—Diisocyanate, 3,3' — Dimethoxydiphenylmethane-1,4'-diisocyanate, 4,4 ; -Jetoxydiphenylmethane-4,4'-diisocyanate, tolylenediisocyanate, 1,5-naphthylenediisocyanate, xylylenedicene And dimer or trimer of each of the above-mentioned isocyanate compounds (e.g., a dimer of hexamethylene diisocyanate). Hexamethylene diisocyanate 3 moles of adduct, 2,4 tolylene diisocyanate 2 monolayers of adduct, 2, 4 — Tolylene diisocyanate, 3 mol of adduct, etc.), two or more different isocyanates selected from these isocyanates, and diisocyanates and dihydric or trihydric polyalcohols ( For example, diethylene glycol, polyethylene glycolone, dipropylene glycolone, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, etc. And the like (eg, adducts of tolylene disocyanate and trimethylolpropane, adducts of hexamethylene diisocyanate and trimethylolpropane, etc.). In addition, these isocyanate compounds may be used alone or in combination of two or more.
さらに、本発明において上述のィソシァネート基を有する化合物として 3個以上 のイソシァネート基を分子内に有し、イソシァネート基の占める割合が化合物中 3 0質量％以上 65質量％以下であるようなィソシァネート化合物を用いることに より後述で、詳述するホログラフィック露光前後の記録メディァの収縮を防止する ことができるのでより好ましい。 _  Further, in the present invention, as the above-mentioned compound having an isocyanate group, an isocyanate compound having three or more isocyanate groups in a molecule and the proportion of the isocyanate group in the compound is 30% by mass or more and 65% by mass or less is used. It is more preferable to use it because the shrinkage of the recording medium before and after the holographic exposure described later can be prevented. _
このような 3個以上のィソシァネート基を分子内に有し、イソシァネート基の占 める割合が化合物中 30質量％以上 65質量％以下であるようなイソシァネート 化合物としては、この条件を満たすィ匕合物であれば特に制限なく用いることができ、 例えば、 1, 8—ジイソシァネート— 4-イソシァネートメチル—オクタン （NCO含 有量： 50. 2質量0 /0、 分子量： 251. 3)、 2 -イソシァネートェチル -2， 6 - ジイソシァネート力プロエート（NCO含有量： 49. 8質量％、分子量： 253. 2)、 ベンゼン— 1, 3， 5—トリイソシァネート （N CO含有量： 62. 7質量0 /0、 分子量： 201. 1)、 1—メチルベンゼン— 2， 4, 6—トリイソシァネート （NC 0含有量： 58. 6質量0 /0、 分子量： 215. 2)、 1, 3, 5-トリメチルベンゼ ン— 2, 4, 6—トリイソシァネート （NCO含有量： 51. 8質量％、 分子量： 2 43. 2)、 ジフエニルメタン— 2, 4, 4' —トリイソシァネート （NCO含有量： 43. 3質量0 /0、 分子量： 291. 3)、 トリフエニルメタン—4, 4' , 4 ート リイソシァネート （NCO含有量： 34. 3質量0 /0、 分子量： 367. 4)、 ビス (イソシア^ "一ト トリル） フエニルメタン （NCO含有量： 42. 6質量0 /0、 分子 量： 2 9 1 . 3 ) などを挙げることができる。 Such an isocyanate compound having three or more isocyanate groups in the molecule and in which the proportion of the isocyanate group occupying the compound is 30% by mass or more and 65% by mass or less in the compound is a compound that satisfies this condition. it can be used without particular limitation so long as, for example, 1, 8- Jiisoshianeto - 4-iso Xia sulfonate methyl - octane (NCO containing Yuryou: 50.2 mass 0/0, molecular weight: 251.3), 2 -Isocyanateethyl -2,6-diisocyanate-proate (NCO content: 49.8% by mass, molecular weight: 253.2), benzene-1,3,5-triisocyanate (NCO content: 62.7 mass 0/0, molecular weight: 201.1), 1-methyl benzene - 2, 4, 6-tri iso Xia sulfonate (NC 0 content: 58.6 mass 0/0, molecular weight: 215.2) 1,3,5-trimethylbenzene—2,4,6-triisocyanate (NCO content: 51.8 mass , Molecular weight: 2 43.2), diphenylmethane - 2, 4, 4 '- tri iso Xia sulfonate (NCO content: 43.3 mass 0/0, molecular weight: 291.3), triphenylmethane -4, 4' , 4-preparative Riisoshianeto (NCO content: 34.3 mass 0/0, molecular weight: 367.4), bis (isocyanatomethyl ^ "Ichito tolyl) phenylmethane (NCO content: 42.6 mass 0/0, the molecule Amount: 291.3).
なお、前述のィソシァネート化合物において、後述で詳述するホログラフィック 記録用組成物で構成した記録層を積層したホログラフィック記録メディアに情報 を全て記録し、この記録し終えた状態で用いられるホログラフィック情報メディア は、 C Dや D V同様に蛍光灯下、窓辺あるいは放置される環境温度が種々多様とな る可能性がある。したがって、種々の条件で記録層の着色を抑えるものが好ましく、 このように着色を抑える為には、上述の化合物の中で脂肪族系のィソシァネート化 合物がより好ましい。  In the above-mentioned isocyanate compound, all information is recorded on a holographic recording medium in which a recording layer composed of a holographic recording composition described in detail below is laminated, and the holographic information used after the recording is completed. Media, like CDs and DVs, can have a variety of ambient temperatures under fluorescent lights, windowsills, or left behind. Therefore, it is preferable that the coloring of the recording layer is suppressed under various conditions, and to suppress the coloring in this way, among the above-mentioned compounds, the aliphatic isocyanate compound is more preferable.
本発明では、上述の必須成分であるィソシァネート基を有する化合物の自己架橋 でバインダーを形成させても良いが、バインダ一形成を温和な条件下で行わせる為 には、上述で詳述したィソシァネート化合物のィソシァネート基と反応する官能基 を分子内に有する化合物との架橋反応によりバインダー形成するのが好ましく、こ のようなィソシァネート化合物と反応しうる化合物としては、例えば分子内に水酸 基を有する化合物、一級または二級アミノ基を有する化合物さらにはェナミン構造 を有する化合物などを挙げることができる。 しかしながら、後述で詳述するホログ ラフィック記録用組成物で構成した記録層を積層したホログラフィック記録メデ ィ了に情報を全て記録し、この記録し終えた状態で用いられるホログラフィック情 報メディアの着色を抑える為には、上述の化合物の中でィソシァネート化合物と反 応しうる化合物として水酸基を有する化合物が好ましく、さらには脂肪族系のアル コール性水酸基を分子内に 2個以上有する化合物がより好ましレ、。また、後で詳述 する本発明のホログラフィック記録メディアを作製する際に、常温で液状或いは 1 0 0 °C以下の温度で液状の記録用組成物を二枚の基材間に所定の厚みで挟持させ ることにより作製されるため、常温で液状或いは融点が 1 0 0 °C以下の化合物がよ り好ましい。 In the present invention, the binder may be formed by self-crosslinking of the compound having an isocyanate group, which is an essential component described above. However, in order to form the binder under mild conditions, the isocyanate compound described in detail above is required. It is preferable to form a binder by a cross-linking reaction with a compound having a functional group that reacts with the isocyanate group in the molecule. Examples of such a compound that can react with the isocyanate compound include a compound having a hydroxyl group in the molecule. And compounds having a primary or secondary amino group, and compounds having an enamine structure. However, all the information is recorded on the holographic recording medium in which the recording layer composed of the holographic recording composition described in detail below is laminated, and the holographic information medium used after the recording is completed is colored. In order to suppress the occurrence of such a compound, a compound having a hydroxyl group is preferable as a compound capable of reacting with the isocyanate compound, and a compound having two or more aliphatic alcoholic hydroxyl groups in the molecule is more preferable. Masure, When producing the holographic recording medium of the present invention, which will be described in detail later, a liquid composition at room temperature or a liquid composition at a temperature of 100 ° C. or less is provided with a predetermined thickness between two substrates. Since it is produced by being sandwiched between layers, compounds that are liquid at room temperature or have a melting point of 100 ° C or less are often used. Is more preferable.
このように分子内にアルコール性水酸基を 2個以上有する化合物としては、例え ばジエチレングリコー^ トリエチレングリコー^/、 ポリエチレングリコーノレ、 ジ プロピレングリコール、 トリプロピレングリコール、 ポリプロピレングリコール、 2， 2—ジメチルー 1 , 3—プロパンジォーノレ、 2 , 2—ジェチルー 1， 3 -プロパンジ オール、 2 -ブチノレ- 2—ェチノレー 1 , 3 _プロパンジォーノレ、 1 , 2—ブタンジォーノレ、 1 , 4 -ブタンジオール、 ポリテトラメチレングリコール、 1 , 5 -ペンタンジォー ノレ、 2—メチルー 2， 4 ~~ペンタンジォ一ノレ、 3 -メチノレ- 1 , 5 -ペンタンジオール、 1 , 6 -へキサンジオール、 2 -ェチノレ- 1， 3 -へキサンジォーノレ、 2 , 5—ジメチ ル— 2， 5 -へキサンジオール、 1， 1 0-デカンジオール、 1 , 4—シクロへキサン ジオール、 グリセリン、 1， 2， 6 -へキサントリオール、 トリメチロールェタン、 トリメチロールプロパン、 ペンタエリスルトール、 ソルビトール等が挙げられ、 さ らに前記分子内にアルコール性水酸基を 2個以上有する化合物を、例えばェチレン グリコーノレ、 ジエチレングリコーノレ、 トリエチレングリコール、 ポリエチレングリ コーノレ、 プロピレングリコーノレ、 ジプロピレングリコーノレ、 トリプロピレングリコ ール、 ポリプロピレングリコール、 ポリテトラメチレングリコールなど 2価のアル コールで変性したアルコールなどが挙げられる。 尚、 これらのアルコール性水酸基 を分子内に 2個以上有する化合物は、 1種単独でも 2種以上を組み合わせて用いて も良い。  Such compounds having two or more alcoholic hydroxyl groups in the molecule include, for example, diethylene glycol ^ triethylene glycol ^ /, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2,2-dimethyl-1 , 3-propanediole, 2,2-getyl-1,3-propanediol, 2-butynole-2-ethyneol 1,3_propanediole, 1,2-butanediole, 1,4-butanediol , Polytetramethylene glycol, 1,5-pentanedionole, 2-methyl-2,4- ~ pentanediole, 3-methinole-1,5-pentanediol, 1,6-hexanediol, 2-ethynol-1, 3-hexanediolone, 2,5-dimethyl-2,5-hexanediol, 1,10-decanediol, 1,4-cyclo Xandiol, glycerin, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc., and further having two or more alcoholic hydroxyl groups in the molecule The compound was modified with a divalent alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Alcohol and the like. These compounds having two or more alcoholic hydroxyl groups in the molecule may be used alone or in combination of two or more.
なお、脂肪族系のアルコール性水酸基を分子内に 2個以上有する化合物の分子量 としては、化合物自身の揮発性、エチレン性不飽和結合を有する化合物、 カチオン 重合可能な官能基を有する化合物あるいは光重合開始剤との相溶性や溶解性を考 慮した場合、通常分子量が 1 0 0以上 2 0 0 0以下にするのが好ましく、 また、脂 肪族系のアルコール性水酸基を分子内に 2個以上有する化合物の添加量としては、 上述の必須成分であるィソシァネート化合物の種類や添加量により一概に規定す ることはできないが、イソシァネート基を有する化合物が有するホログラフィック 記録用組成物中のイソシァネート基のモル数を N [m o 1 ]、 前記アルコール性水. 酸基を化合物のホログラフィック記録用組成物中の水酸基のモル数を M [m o 1 ] とした際に、 通常 0 . 5≤NZM≤2 . 0であり、 より好ましくは 0 . 7≤N/M ≤ 1 . 5の範囲にするのが相溶性や架橋反応のコントロールの面からより好ましレ、。 さらに、本発明では前述したィソシァネート基を有する化合物とアルコール性水 酸基を分子内に 2個以上有する化合物を反応させてウレタン結合を形成させる際 に、低温で反応を行いたい場合には、 ウレタン硬化触媒として錫、鉛等の公知の有 機金属化合物を添加するのが好ましい。 The molecular weight of a compound having two or more aliphatic alcoholic hydroxyl groups in a molecule may be a compound having a volatility of the compound itself, a compound having an ethylenically unsaturated bond, a compound having a cationically polymerizable functional group, or a photopolymerization. In consideration of the compatibility and solubility with the initiator, it is usually preferable that the molecular weight is 100 or more and 200 or less. The amount of the compound having two or more aliphatic alcoholic hydroxyl groups in the molecule cannot be specified unconditionally by the type and amount of the isocyanate compound, which is an essential component described above, but the amount of the compound having an isocyanate group The mole number of the isocyanate group in the holographic recording composition of the compound is N [mo 1], and the alcoholic water. The mole number of the hydroxyl group in the holographic recording composition of the compound is M [mo 1 ], It is usually 0.5 ≤ NZM ≤ 2.0, and more preferably 0.7 ≤ N / M ≤ 1.5 in terms of compatibility and control of crosslinking reaction. I like it. Furthermore, in the present invention, when a compound having an isocyanate group and a compound having two or more alcoholic hydroxyl groups in a molecule are reacted to form a urethane bond, the urethane bond may be reacted at a low temperature. It is preferable to add a known organic metal compound such as tin or lead as a curing catalyst.
また、ォキシラン基を有する化合物とメルカプタン基を有する化合物を重合させ てバインダーを形成する場合に用いられる分子内にォキシラン基を有する化合物 やメルカブタン基を有する化合物としては、架橋可能な公知の化合物を特に制限な く使用することができがる力 後で詳述する本発明のホログラフィック記録メディ ァを作製する際に、常温で液状或いは 1 0 0 °C以下の温度で液状の記録用組成物を 二枚の基材間に所定の厚みで挟持させることにより作製されるため、常温で液状或 いは融点が 1 0 0 °C以下の化合物が好ましく、さらにはォキシラン基あるいはメル カブタン基を 2個以上有する化合物がより好ましい。  In addition, as the compound having an oxysilane group or the compound having a mercaptan group in a molecule used in forming a binder by polymerizing a compound having an oxysilane group and a compound having a mercaptan group, a known crosslinkable compound is particularly preferable. Force that can be used without limitation When producing the holographic recording medium of the present invention described in detail below, the recording composition which is liquid at room temperature or liquid at a temperature of 100 ° C or less is used. Since it is produced by sandwiching it with a predetermined thickness between two substrates, a compound that is liquid at room temperature or has a melting point of 100 ° C. or less is preferable, and two oxysilane groups or mercaptan groups are more preferable. Compounds having the above are more preferred.
上述したォキシラン基を有する具体的化合物としては、脂肪族ポリグリシジルェ 一テル、 ポリアルキレングリコールジグリシジルエーテル、 3級カルボン酸モノグ リシジルエーテル、 ビスフエノール Aとェピクロルヒドリンとの重縮合物、水添ビ スフエノール Aとェピクロルヒ ドリンとの重縮合物、臭素化ビスフエノール Aとェ ピクロルヒ ドリンとの重縮合物およびビスフエノール Fとェピクロルヒ ドリンと の重縮合物などの末端がグリシジル基で変性された樹脂、グリシジル変性フエノー ルノボラック樹脂、グリシジル変性 0 -クレゾールノポラック樹脂などが挙げられ、 更には 「1 1 2 9 0の化学商品」 化学工業日報社， 7 7 8— 7 8 7頁に記載の化合 物なども好適に用いることができ、このような分子内にォキシラン基を有する化合 物は必要に応じて 2種以上併用して用いてもよい。 Specific examples of the above-mentioned compound having an oxysilane group include aliphatic polyglycidyl ether, polyalkylene glycol diglycidyl ether, tertiary carboxylic acid monoglycidyl ether, and polycondensate of bisphenol A and epichlorohydrin. , Polycondensation product of hydrogenated bisphenol A and epichlorohydrin, brominated bisphenol A and A resin having a terminal modified with a glycidyl group, a glycidyl-modified phenol novolak resin, a glycidyl-modified 0-cresol nopolak resin, and the like, such as a polycondensate with piclorhydrin and a polycondensate with bisphenol F and epichlorohydrin. Further, the compounds described in “Chemical Products of 112,900”, Kagaku Kogyo Nippo Co., Ltd., pp. 778-787 can also be suitably used, and such compounds having an oxysilane group in the molecule can be used. The substances may be used in combination of two or more if necessary.
また、 メルカプタン基を有する化合物としては、 例えば、 チォグリコール酸、 チ ォグリコール酸アンモニゥム、 チォグリコール酸モノエタノールァミン、チォグリ コール酸ソーダ、 チォグリコール酸メチル、 チォグリコール酸ォクチル、 チォグリ コール酸メ トキシブチル、 ブタンジオールビスチォグリコレート、エチレングリコ 一^/ビスチォグリコレート、 トリメチローノレプロパントリスチォグリコレート、ぺ ンタエリスリ トールテトラキスチォグリコレート、 3 -メルカプトプロピオン酸、 メルカプトプロピオン酸メチル、 メルカプトプロピオン酸ォクチル、 メルカプトプ 口ピオン酸メ トキシプチル、 メルカプトプロピオン酸トリデシル、 ブタンジオール ビスチォプロピオネート、エチレングリコールビスチォプロピオネート、 トリメチ ロールプロパントリスチォプロピオネート、ペンタエリスリ トールテトラキスチォ プロピオネート、ジペンタエリスリ トールやトリメチロールプロパン等の多価アル コールとメルカプトプロピオン酸とのエステル等が挙げられる。これらチオール含 有化合物は、 単独で用いてもよく、 2種以上を併用してもよい。  Examples of the compound having a mercaptan group include, for example, thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolate, sodium thioglycolate, methyl thioglycolate, octyl thioglycolate, and methoxybutyl thioglycolate. , Butanediol bisthioglycolate, ethyleneglycol 1 / bisthioglycolate, trimethylonolepropanetristhioglycolate, pentaerythritol tetrakisthioglycolate, 3-mercaptopropionic acid, methyl mercaptopropionate, octyl mercaptopropionate , Mercaptopop Methoxybutyl thionate, tridecyl mercaptopropionate, butanediol bisthiopropionate, ethylene glycol bisthiopropione And esters of mercaptopropionic acid with polyvalent alcohols such as trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, dipentaerythritol and trimethylolpropane. These thiol-containing compounds may be used alone or in combination of two or more.
さらに、ォキシラン基を有する化合物とメルカプタン基を有する化合物を重合さ せてパインダーを形成する場合には、より温和な条件で重合させる為にプレンステ ッド塩基やルイス塩基を含有させるのが好ましく、このような塩基としては例えば、 ピリジン、 ピぺリジン、 ジメチルァニリン、 2， 4 , 6 -トリス （ジメチルァミノ メチル） ベンゼン、 2， 4 , 6 -トリス （ジメチルァミノメチル） フエノールなど のァミン化合物を挙げることができる。 Further, when a compound having an oxysilane group and a compound having a mercaptan group are polymerized to form a binder, it is preferable to include a prensted base or a Lewis base in order to perform polymerization under milder conditions. Such bases include, for example, pyridine, piperidine, dimethylaniline, 2,4,6-tris (dimethylamino Amines such as methyl) benzene and 2,4,6-tris (dimethylaminomethyl) phenol.
また、本発明の必須成分として記録層に添加される上述の一般式（1 ) で表され る光重合開始剤において、式中 Aで表される無置換またはアルキル基置換シクロぺ ンタ ェニル基とは、シク口ペンタジェニル基に結合するものが水素またはアルキ ル基であることを指す。なおここで言うアルキル基の数はシク口ペンタジェニル基 にたいして 0— 5個であり、 またアルキル基としては炭素数 1一 1 2の直鎖、分岐 あるいは環状のものが好ましい。 さらに、式中; Bで表される無置換または置換ァレ ーン基とは、 ベンゼン、 ナフタレン、 アントラセン、 フエナントレン、 タリセン、 ピレン、 トリフエ二レン、ペリレンあるいはフルオレンなどのベンゼン環を少なく とも有する無置換または置換基を有する化合物を指し、該ァレーン基の置換基とし ては炭素数 1一 1 2の直鎖、 分岐あるいは環状のアルキル基、 _O R、 -C O R , - C O O Rなどを挙げられ、前述の Rは炭素数 1一 1 2の直鎖、分岐あるいは環状の アルキル基を表す。 また、 式中 X—で表される対ァニオンとしては、 ハロゲンィォ ン、 硝酸イオン、 へキサフノレオ口アンチモネート、 へキサフノレオ口ホスフェート、 トリフレート、テトラフルォロボレ一ト、ペンタフルォロヒ ドロキシアンチモネ一 トなどを挙げることができる。  Further, in the photopolymerization initiator represented by the above general formula (1) added to the recording layer as an essential component of the present invention, an unsubstituted or alkyl-substituted cyclopentenyl group represented by A in the formula is used. Indicates that the one bonded to the cycle pentagenenyl group is hydrogen or an alkyl group. The number of alkyl groups mentioned here is 0 to 5 with respect to the pentagenenyl group having a mouth, and the alkyl group is preferably a straight-chain, branched or cyclic one having 11 to 12 carbon atoms. Further, in the formula, the unsubstituted or substituted arylene group represented by B is a non-substituted or substituted arylene group having at least a benzene ring such as benzene, naphthalene, anthracene, phenanthrene, thalicene, pyrene, triphenylene, perylene or fluorene. Refers to a compound having a substituent or a substituent. Examples of the substituent of the arene group include a straight-chain, branched or cyclic alkyl group having 11 to 12 carbon atoms, _OR, -COR, -COOR, and the like. R represents a linear, branched or cyclic alkyl group having 11 to 12 carbon atoms. In the formula, the anion represented by X— includes halogen, nitrate ion, hexafenoleo antimonate, hexafenoleo phosphate, triflate, tetrafluoroborate, and pentafluorohydroxyantimonate. And the like.
このような一般式 （1 ) で表される具体的なものとしては、 例えば ( η 6 -m- キシレン） （77 5—シクロペンタジェニル）鉄（1 +) テトラフルォロボレート、 ( η 6— 0—キシレン） （ 5—シクロペンタジェニル） 鉄 （1 +) トリフレート、 （η 6— ο -キシレン) ( η 5—シクロペンタジェニル) 鉄 （1 +) へキサフルォロアンチモ ネート、 （77 6— ρ—キシレン類). 5—シクロペンタジェニル） 鉄 （1 +) トリフ レート、 6—ァセトフエノン） 5—メチルシクロペンタジェニル） 鉄 （1 +) へキサフルォロアンチモネート、 6-キシレン類 （混合異性体）） 5-シクロ ペンタジェ -ル）鉄（1 +)へキサフルォロアンチモネ一ト、 ( η 6 -キシレン類 (混 合異性体）） ( η 5-シクロペンタジェ二ル） 鉄 （1+) へキサフルォロホスフヱ一 ト、 （？76—タメン） （775-シク口ペンタジェニル) 鉄 （1+) へキサフルォロアン チモネ一ト、 ( 776—クメン) (?7 5 -シクロペンタジェニル) 鉄 （1 +) へキサフル ォロホスフヱート、 6—タメン） 5—シクロペンタジェニル） 鉄 （1 +) へキ サフルォロアルセネート、 ( η 6 -クリセン) ( η 5 -シク口ペンタジェニル) 鉄 （1 + ) ペンタフノレォロヒ ドロキシアンチモネート、 （7J 6—トノレェン） （775—シクロべ ンタジェニル） 鉄 （1 +) へキサフノレオロアルセネート、 (776—トノレエン） （？75- シクロペンタジェ二 Λ^) 鉄 （1 +) へキサフノレオ口アンチモネート、 （77 6—ナフタ レン) (?7 5—シクロペンタジェニル） 鉄 （1 +) テトラフルォロボレート、 ( 6 - ピレン） ( η 5—シクロペンタジェニル） 鉄 （1 +) トリフレート、 6—フルォレ ン） 5—シクロペンタジェニル）鉄（1+)へキサフルォロアンチモネ一ト、 6—へキサメチルベンゼン） ( 77 5—シクロペンタジェニル) 鉄 （1 +) ペンタフル ォロヒ ドロキシアンチモネート、 6—ペリレン） （7 5—シクロペンタジェニル） 鉄 （1 +) へキサフルォロアンチモネート、 （ 6—ベンゼン） （ 5-シクロペンタ ジェ -ル） 鉄 （1+) へキサフルォロアンチモネ一ト、 ( η 6—メシチレン） （775 - シクロペンタジェ二ノレ） 鉄 （1 +) へキサフノレオ口アンチモネート、 （77 6—メシチ レン） （77 5-シクロペンタジェニル） 鉄 （1 +) へキサフルォロホスフェート、 及 び （ 776—メシチレン） ( η 5—シクロペンタジェニル) 鉄 （1 +) ペンタフルォロ ヒドロキシアンチモネートなどを挙げることができる。 Specific examples of such a compound represented by the general formula (1) include, for example, (η 6 -m-xylene) (775-cyclopentagenenyl) iron (1 +) tetrafluoroborate, (η 6-0-xylene) (5-cyclopentagenenyl) iron (1+) triflate, (η6-o-xylene) (η5-cyclopentagenenyl) iron (1+) hexafluoroantimo , (776-ρ-xylenes). 5-cyclopentagenenyl) iron (1 +) triflate, 6-acetophenone) 5-methylcyclopentagenenyl) iron (1 +) Hexafluoroantimonate, 6-xylene (mixed isomer)) 5-cyclopentagel) iron (1+) hexafluoroantimonate, (η 6-xylene (mixed isomer) body)) (η 5- cyclopentadienyl Jefferies yl) iron (1+) to Kisa full O Russia phosphine We one door, (? 76- multifaceted) (775- consequent opening Pentajeniru) Kisafuruoroan Chimone one to iron (1+) (776-cumene) (? 7 5-cyclopentagenenyl) iron (1 +) hexafluorophosphate, 6-tamene) 5-cyclopentagenenyl) iron (1 +) hexafluoroarsenate, (η 6 -chrysene) (η 5 -cyclohexapentagenenyl) iron (1 +) pentaphenylenohydroxy hydroxyantimonate, (7J 6 -tonolene) (775 -cyclopentenyl) iron (1 +) hexafenoleo Loarsenate, (776-tonolene) (? 75-cyclopentadi (2Λ ^) iron (1 +) hexafenole antimonate, (776-naphthalene) (? 75-cyclopentagenenyl) iron (1 +) tetrafluoroborate, (6-pyrene) (η 5-cyclopentagenenyl) iron (1+) triflate, 6-fluorene 5-cyclopentagenenyl) iron (1+) hexafluoroantimonate, 6-hexamethylbenzene) ( 77 5-cyclopentagenenyl) iron (1+) pentafluorohydroxyantimonate, 6-perylene) (75-cyclopentagenenyl) iron (1+) hexafluoroantimonate, (6-benzene ) (5-cyclopentagel) iron (1+) hexafluoroantimonate, (η6-mesitylene) (775-cyclopentageninole) iron (1+) hexafenoleoantimonate, (77 6-mesitylene) (77 5-cyclopentageni ) Iron (1 +) to the hexa full O b phosphate, 及 Beauty (776- mesitylene) (eta 5-cyclopentadienyl) iron (1 +) Pentafuruoro hydroxy antimonate and the like.
詳述した一般式 （1) で表される光重合開始剤において、 式中 Χ_で表される対 ァ-オンとしてフッ素原子を含有する対ァユオンが、錯体自体のの安定性、記録層 形成組成物を調製する際の液安定性、さらには光重合開始剤としてより有効にラジ カルを生成できることから好ましい。 In the photopolymerization initiator represented by the general formula (1) described in detail, the aion containing a fluorine atom as the aion represented by Χ_ in the formula represents the stability of the complex itself and the recording layer. It is preferable because the liquid stability at the time of preparing the forming composition and the radical can be more effectively generated as a photopolymerization initiator.
本発明のェチレン性不飽和結合を有する化合物を光重合させる為の光重合開始 剤は、 上述で詳述した一般式 （1 ) で表される化合物の他に、 従来から公知の、 ベ ンゾィン及びその誘導体、ベンゾフエノンなどのカルボニル化合物、了ゾビスィソ ブチロニトリルなどのァゾ化合物、ジベンゾチアゾリルスルフィ ドなどの硫黄化合 物、 ベンゾィルパーォキシドなどの過酸化物、 2 -トリブロモメタンスルホ二ル- ピリジンなどのハロゲン化物、四級アンモ-ゥム塩或いは置換または無置換のジフ ヱ二ルョードニゥム塩、 トリフエニルスルホニゥム塩などのォニゥム化合物、 2 , 2 -ビス ( o—クロロフエ二ル） —4， 4，， 5 , 5， ーテトラフエニノレビイミダゾー ルなどのビスィミダゾール化合物、チタノセン錯体などの金属 π錯体などの光重合 開始剤を併用しても良く、さらに後述で述べるホログラフィック露光する際に用い る露光光源波長に対して、該光重合開始剤のホログラフィック露光に使用されるレ 一ザ一光源の波長に対して吸収を持たない、或いは持っていたとしても極僅かで有 る場合には、光重合開始剤の分光波長を波長增感させるための増感色素を併用する のがより好ましい。  The photopolymerization initiator for photopolymerizing the compound having an ethylenic unsaturated bond of the present invention includes, in addition to the compound represented by the general formula (1) described in detail above, benzoin and benzoin, which are conventionally known. Its derivatives, carbonyl compounds such as benzophenone, azo compounds such as azobisisobutyronitrile, sulfur compounds such as dibenzothiazolyl sulfide, peroxides such as benzoyl peroxide, 2-tribromomethanesulfonyl- Halides such as pyridine, quaternary ammonium salts or onium compounds such as substituted or unsubstituted diphenylbenzene salts and triphenylsulfonium salts, 2,2-bis (o-chlorophenyl) —4 Photopolymerization of bisimidazole compounds such as 1,4,5,5, -tetrapheninolebiimidazole and metal π complexes such as titanocene complexes An initiator may be used in combination, and the wavelength of an exposure light source used for holographic exposure described later and the wavelength of a laser light source used for holographic exposure of the photopolymerization initiator may be used. When the photopolymerization initiator has no absorption or has very little absorption, it is more preferable to use a sensitizing dye for making the spectral wavelength of the photopolymerization initiator sensitive to the wavelength.
尚、ここで用いる光重合開始剤の分光波長を波長増感させるための増感色素とし ては当分野で使用されている各種色素を挙げることができ、例えばタマリン誘導体、 メチン誘導体、ポリメチン誘導体、トリァリールメタン誘導体、インドリン誘導体、 ァジン誘導体、 チアジン誘導体、 キサンテン誘導体、 チォキサンテン誘導体、 ォキ サジン誘導体、 アタリジン誘導体、 シァニン誘導体、 カルボシァニン誘導体、 メロ シァニン誘導体、へミシァニン誘導体、ローダシァニン誘導体、ァザメチン誘導体、 スチリル誘導体、 ピリリゥム誘導体、 チォピリリゥム誘導体、 ボルフイラジン誘導 体、 ボルフィリン誘導体、 フタ口シァニン誘導体及ぴピロメテン誘導体等の各種色 素を単独或いは必要に応じて二種以上併用して用いても良い。 As the sensitizing dye for sensitizing the spectral wavelength of the photopolymerization initiator used here, various dyes used in the art can be mentioned.For example, tamarin derivatives, methine derivatives, polymethine derivatives, Triarylmethane derivative, indoline derivative, azine derivative, thiazine derivative, xanthene derivative, thioxanthene derivative, oxazine, ataridine derivative, cyanine derivative, carbocyanine derivative, melocyanin derivative, hemicyanin derivative, rhodocyanin derivative, azamethine derivative, styryl derivative , Pyrylium derivatives, thiopyrylium derivatives, vorphyrazine derivatives Various colorants such as a compound, a porphyrin derivative, a phthalocyanine derivative and a pyromethene derivative may be used alone or in combination of two or more as needed.
このような光重合開始剤または増感色素の具体的なものとしては、例えば米国特 許第 5, 027, 436号、 同 5， 096, 790号、 同 5， 147, 758号、 同 5, 204, 467号、 同 5， 256, 520号、 同 6， 01 1， 180号、 欧 州特許第 255， 486号、同 256, 981号、同 277, 915号、同 318, 893号、同 401， 165号、同 565， 488号、特開平 2— 236553号、 同 5— 46061号、 同 5— 216227号、 同 5— 2471 10号、 同 5— 2572 79号、 同 6— 175554号、 同 6— 1 75562号、 同 6— 175563号、 同 6— 175566号、 同 6— 1 86899号、 同 6— 195015号、 同 6— 2025 40号、 同 6— 202541号、 同 6— 202543号、 同 6— 202544号、 同 6 - 202548号、 同 6— 324615号、 同 6— 329654号、 同 7— 1347 3号、 同 7— 28379号、 同 7— 84502号、 同 7— 84503号、 同 7— 181 876号、 同 9— 106069号、 同 9— 309907号、 特開 2002— 6042 9号、 同 2002-62786号、 同 2002— 244535号等明細書に記載され ているものを適時選択して用いることができる。  Specific examples of such photopolymerization initiators or sensitizing dyes include, for example, US Pat. Nos. 5,027,436, 5,096,790, 5,147,758, 5, Nos. 204, 467, 5, 256, 520, 6, 01 1, 180, European Patent Nos. 255, 486, 256, 981, 277, 915, 318, 893, Nos. 401, 165, 565, 488, JP-A-2-236553, 5-46061, 5-216227, 5-247110, 5-25779, 6-175554, 6-175554, 6-1 75562, 6-175563, 6-175566, 6-186899, 6-195015, 6-202540, 6-202541, 6-202543 6-202544, 6-202548, 6-324615, 6-329654, 7-13347, 7-28379, 7-84502, 7-84503, 7-84503, No. 7-181 876, No. 9-106069, No. 9-309907, JP 2002-60429, No. 2002-62786, No. 2002- Those described in the specification such as 244535 can be appropriately selected and used.
上述したエチレン性不飽和結合を有する化合物を光重合させる為の光重合開始 剤としては、光重合開始剤の分子量やエチレン性不飽和結合を有する化合物中のェ チレン性不飽和結合の占める割合により一概に決めることはできないが、通常ェチ レン性不飽和結合を有する化合物に対して通常 0. 01質量部一 25質量部の範囲 で用いるのが好ましい。 また、光重合開始剤を分光増感することができる増感色素 は色素自身の分子量やモル吸光係数により一概に規定することはできないが、通常 光重合開始剤に対して通常 0. 01— 25質量部の範囲で用いるのが好ましい。 本発明においては、前述したバインダ一形成化合物から形成されるパインダ一に 対して、拡散重合で得られるエチレン性不飽和結合を有する化合物の重合体との屈 折率差をより顕著に持たせるためには、該エチレン性不飽和結合を有する化合物の 屈折率としてバインダー形成化合物よりも高いものを用いるカ 或いは低いものを 用いるのが好ましい。特にエチレン性不飽和結合を有する化合物として屈折率が 1 . 5 5以上の化合物を用いることが高屈折率のエチレン性不飽和結合を有する化合 物の重合体が得られること力 ら好ましく、その際はパインダ一形成化合物としては 屈折率,が 1 . 5 0前後の化合物を用いるのが好ましい。 The photopolymerization initiator for photopolymerizing the compound having an ethylenically unsaturated bond described above depends on the molecular weight of the photopolymerization initiator and the ratio of the ethylenically unsaturated bond in the compound having an ethylenically unsaturated bond. Although it cannot be unconditionally determined, it is usually preferred to use 0.01 to 25 parts by mass of the compound having an ethylenically unsaturated bond. A sensitizing dye capable of spectrally sensitizing a photopolymerization initiator cannot be unconditionally defined by the molecular weight of the dye itself or the molar extinction coefficient, but is usually 0.01 to 25 to the photopolymerization initiator. It is preferably used in the range of parts by mass. In the present invention, in order to give a more significant difference in the refractive index between the binder formed from the binder-forming compound described above and the polymer of the compound having an ethylenically unsaturated bond obtained by diffusion polymerization. Preferably, the compound having an ethylenically unsaturated bond has a refractive index higher or lower than that of the binder-forming compound. In particular, it is preferable to use a compound having a refractive index of 1.55 or more as a compound having an ethylenically unsaturated bond, since a polymer of a compound having an ethylenically unsaturated bond having a high refractive index can be obtained. It is preferable to use a compound having a refractive index of about 1.5 as a binder-forming compound.
このような、 屈折率が 1 . 5 5以上の （メタ） ァクリロイル基を有する化合物と しては、 一般に分子内に窒素、 酸素、 硫黄およびリンなどのへテロ原子、 塩素、 臭 素およびョゥ素などのハロゲン原子、あるいは芳香環を二価以上有する化合物が挙 げられ、 このような化合物の具体的なものとしては、パラクミルフエノキシェチレ ングリコールァクリレート、パラクミルフエノキシエチレングリコールメタァクリ レート、 ヒ ドロキシェチル化 0—フエ-ルフエノールァクリレート、 ヒ ドロキシェ チル化] 3—ナフトールアタリ レート、 トリブルモフエ二ルアタリレート、 トリプノレ モフエニルメタァクリ レート、 トリョードフエニルメタクリ レート、 ポリエチレン ォキサイド変性テトラプロモビスフエノール Aジァクリレート、ポリエチレンォキ サイド変性テトラブロモビスフエノール Aジメタタリレート、 ビス （4-メタクリ ロイルチオフエニル） スルフィド、特開平 6— 3 0 1 3 2 2号、特開 2 0 0 0 - 3 4 4 7 1 6号、 同 2 0 0 3 - 2 9 6 0 4号等に記載されたフルオレン骨格を有する化 合物などを挙げることができる。  Such compounds having a (meth) acryloyl group having a refractive index of 1.55 or more generally include, in the molecule, hetero atoms such as nitrogen, oxygen, sulfur and phosphorus, chlorine, bromine and boron. Compounds having a divalent or higher valence such as halogen atoms such as silicon or aromatic rings are mentioned. Specific examples of such compounds include paracumylphenoxhetylene glycol acrylate and paracumylphenoxyethylene glycol meta- Acrylate, hydroxylated, 0—phenylphenol acrylate, hydroxyxylated) 3—naphthol acrylate, triblemofenyl acrylate, trypnole mophenyl methacrylate, trydophenyl methacrylate, polyethylene Oxide modified tetrapromobisphenol A diacrylate, Ethylene oxide-modified tetrabromobisphenol A dimethatalylate, bis (4-methacryloylthiophenyl) sulfide, JP-A-6-310132, JP-A-200-344444 And compounds having a fluorene skeleton described in JP-A-2003-29604 and the like.
また、パインダ一形成化合物から形成されたパインダ一とエチレン性不飽和結合 を有する化合物の拡散重合物との間で屈折率差を設けるという目的を阻害しない 範囲で、 ホログラフィック記録層組成物を調製する際の相溶性や粘度調整、 さらに はホログラフィック露光時の拡散重合を制御する等の目的で、屈折率が 1 . 5 5未 満の （メタ） アタリロイル基を有する化合物をさらに添加してもよく、 このような (メタ） ァクリロイル基を する化合物としては、 例えば、 （メタ） アタリロイル 基を 1個有する化合物として置換または無置換のフヱノール、ノ-ルフエノール及 び 2 -ェチルへキサノールの (メタ） アタリレート、 並びにこれらのアルコールの アルキレンォキシド付加物の (メタ） ァクリレート等が挙げられる。 (メタ） ァク リロイル基を 2個有する化合物としては、 置換または無置換のビスフエノール A、 ビスフエノール F、 フルオレン及びイソシァヌル酸のジ (メタ） アタリレート並ぴ にこれらのアルコールのアルキレンォキシド付加物のジ (メタ） アタリレート、 ェ チレングリコーノレやプロピレンダリコーノレなどのポリァノレキレングリコーノレのの ジ (メタ) アタリレートド等が挙げられる。 (メタ) ァクリロイル基を 3個有する 化合物としては、ペンタエリスリ トール、 トリメチロールプロパン及びイソシァヌ ル酸のトリ （メタ） アタリレート、 並びにこれらのアルコールのアルキレンォキシ ド付加物のトリ （メタ） アタリレート等があり、 （メタ） アタリロイノレ基を 4個以 上有する化合物としては、ペンタエリスリ トール、 ジペンタエリスリ トールのポリ (メタ） アタリレート等が挙げられる。 また、 ウレタン結合を主鎖とするウレタン アタリレート、エステル結合を主鎖とするポリエステルァクリレート等の従来公知 の （メタ） アタリロイル基含有系モノマー 'オリゴマーなども本発明においては適 時選択して用いることができる。 In addition, the purpose of providing a refractive index difference between the binder formed from the binder-forming compound and the diffusion polymer of the compound having an ethylenically unsaturated bond is not hindered. (Meta) having a refractive index of less than 1.55 for the purpose of adjusting the compatibility and viscosity when preparing the holographic recording layer composition and controlling diffusion polymerization during holographic exposure. A compound having an atariloyl group may be further added. Examples of such a compound having a (meth) acryloyl group include substituted or unsubstituted phenol and norphenol as a compound having one (meth) atalyloyl group. And (meth) acrylate of 2-ethylhexanol, and (meth) acrylate of alkylene oxide adducts of these alcohols. Compounds having two (meth) acryloyl groups include substituted or unsubstituted bisphenol A, bisphenol F, fluorene and di (meth) acrylate of isocyanuric acid, as well as alkylene oxide addition of these alcohols. Di (meth) acrylates of the product, di (meth) atalylate of polyanylene glycolone such as ethylene glycolone and propylene daricornole, and the like. Compounds having three (meth) acryloyl groups include pentaerythritol, trimethylolpropane and tri (meth) atalylate of isocyanuric acid, and tri (meth) acrylate of an alkylene oxide adduct of these alcohols. Examples of the compound having four or more (meth) atalyleinole groups include pentaerythritol and dipentaerythritol poly (meth) atalylate. In the present invention, a conventionally known monomer (oligomer) containing a (meth) atalyloyl group, such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain, is appropriately selected in the present invention. Can be used.
尚、前述した分子内にエチレン性不飽和結合を有する化合物は、一種単独で用い ても良いし、二種以上を併用しても良く、通常ホログラフィック記録用組成物中 1 . 0質量％以上、 5 0質量％以下でぁり、 さらには 4 . 0質量％以上、 4 0質量％以 下にするのが好ましく、エチレン性不飽和結合を有する化合物を拡散重合させ高屈 折率の重合体を形成させる場合には、分子内にエチレン性不飽和結合を有する化合 物全体に対して、 上述した屈折率が 1 . 5 5以上の化合物を通常 5 0— 1 0◦質 量％含有するのが好ましく、さらには 6 0— 1 0 0質量％含有するのがより好まし い。 The compounds having an ethylenically unsaturated bond in the molecule described above may be used alone or in combination of two or more, and usually at least 1.0% by mass in the holographic recording composition. , 50% by mass or less, and more preferably 4.0% by mass or more, 40% by mass or less. When the compound having an ethylenically unsaturated bond is formed by diffusion polymerization of a compound having an ethylenically unsaturated bond to form a polymer having a high refractive index, The compound having a refractive index of 1.55 or more as described above is usually preferably contained in an amount of 50 to 100% by mass, and more preferably 60 to 100% by mass.
本発明の記録メディアに用いられる第一の基材及ぴ第二の基材としては、透明で あり使用環境温度で伸縮や曲がりを発生しないもの、さらには上述した記録用組成 物に対して不活性なものであれば特に制限なく用いることができ、このような基材 としては、 石英ガラス、 ソーダガラス、 カリガラス、 鉛クリスタルガラス、 ほう珪 酸ガラス、アルミノ珪酸ガラス、チタンクリスタルガラス或いは結晶化ガラスなど のガラス、 ポリカーボネート、 ポリアセタール、 ポリアリレート、 ポリエーテルエ ーテルケトン、 ポリスルホン及ぴポリエーテルスルホン、 ポリイミ ド-ァミ ドゃポ リエーテルィミドなどのポリイミド、ポリアミド、環状ォレフィン系開環重合物な どのポリオレフインなどの各種樹脂を挙げることができる。  The first base material and the second base material used for the recording medium of the present invention are transparent and do not cause expansion or contraction or bending at the ambient temperature of use, and are incompatible with the above-mentioned recording composition. Any active material can be used without particular limitation. Examples of such a substrate include quartz glass, soda glass, potash glass, lead crystal glass, borosilicate glass, aluminosilicate glass, titanium crystal glass, and crystallized glass. Various resins such as glass such as polycarbonate, polyimide such as polycarbonate, polyacetal, polyarylate, polyetheretherketone, polysulfone and polyethersulfone, polyamide-amide-polyetherimide, polyamide, and cyclic olefin ring-opening polymer. Can be mentioned.
前述の基材の中で、ホログラフィック露光する際の環境温度や湿度に対する厚み 変動や気体透過性、ホログラフィック露光時に使用する光源波長の光の透過率の観 点から、情報光及び参照光が入射する側である第一の基材の材質としてはガラスに するのがより好ましい。 また、第二の基材は第一の基材同様、材質としてはガラス が好ましいが、ホログラフィック記録された情報を C C Dで読み出す際に焦点補正 機構を設けた装置であれば、伸縮率や厚み変動が押さえられたガラスのような基材 ではなく樹脂からなる基材であつても良い。  Among the above-mentioned substrates, the information light and the reference light are considered from the viewpoints of thickness fluctuation with respect to environmental temperature and humidity during holographic exposure, gas permeability, and light transmittance of the light source wavelength used during holographic exposure. The material of the first base material on the incident side is more preferably glass. Like the first substrate, the second substrate is preferably made of glass, but if the holographically recorded information is read out by a CCD, a device provided with a focus correction mechanism may be used to expand or contract the thickness or thickness. A substrate made of resin may be used instead of a substrate such as glass whose fluctuation is suppressed.
また、 情報光及び参照光が入射する側の第一の基材の入射する光の透過率は 7 0 %以上が好ましく、さらには 8 0 %以上がホログラフィック記録層に到達する光 のロスが少ないことからより好ましい。このように透過率をなるベく上げるために は、ホログラフィック記録層が積層された面とは反対の第一の基材面に反射防止処 理を施したものが好ましく、このような反射防止処理としては第一の基材ょりも屈 折率が低ければ特に制限はないが、例えば A l F 3、 Mg F 2、 A l F 3 'Mg F 2、 C a F 2等の無機金属フッ化物、 フッ化ビニリデン、 テフロン （R) などのフ ッ素原子を含有するホモポリマー、 コポリマー、 グラフト重合体、 ブロック重合体 さらにはフッ素原子を含有する官能基で修飾した変性ポリマー等の有機フッ化物 などが、基材として前述で詳述したものよりも屈折率が低くなることから好ましい。 尚、基材上にフッ素系の化合物からなる層を設ける方法としては、支持体ゃフッ 素系の化合物の種類により一概に決めることはできないが、 ゾル-ゲル法、 真空蒸 着法、 スパッタリング法、 CVD法或いは塗工法などの公知の方法、或いは特開平 7— 27902号、 特開 2001— 123264号、 同 2001— 264509号公 報等に記載された方法などを適時選択して用いることができる。 The transmittance of light incident on the first substrate on the side where the information light and the reference light are incident is preferably 70% or more, and more preferably 80% or more of the light reaching the holographic recording layer. This is more preferable because of low loss of the resin. In order to increase the transmittance as described above, it is preferable that an anti-reflection treatment is applied to the first substrate surface opposite to the surface on which the holographic recording layer is laminated. The treatment is not particularly limited as long as the refractive index of the first substrate is also low, but for example, inorganic metals such as AlF3, MgF2, AlF3'MgF2, and CaF2 Organic fluorine such as fluoride, vinylidene fluoride, homopolymers, copolymers, graft polymers, block polymers containing fluorine atoms such as Teflon (R), and modified polymers modified with functional groups containing fluorine atoms Compounds and the like are preferable because they have a lower refractive index than those described in detail above as the base material. The method of providing a layer made of a fluorine-based compound on a base material cannot be unequivocally determined depending on the type of the support-fluorine-based compound, but a sol-gel method, a vacuum evaporation method, and a sputtering method A known method such as a CVD method or a coating method, or a method described in JP-A-7-27902, JP-A-2001-123264, JP-A-2001-264509 or the like can be appropriately selected and used. .
このような反射防止層は基材の表面処理や材質などにより一概に規定すること はできないが、 通常 0. 001— 20 の範囲であり、 好ましくは 0. 005— 10 umの範囲である。  Such an antireflection layer cannot be unconditionally defined by the surface treatment or material of the base material, but is usually in the range of 0.001 to 20 and preferably in the range of 0.005 to 10 um.
また、 特開 2002—123949号、 国際公開第 99/5 7719号等のホロ グラフィック記録 ·再生装置に用いられるような記録メディアに対しては、第二の 基材ホログラフィック記録層が積層される面或いはその反対面に反射層が設けら れることが好ましく、このように反射層を設ける場合には反射させる光の波長に対 して反射率を 70 %以上にするのが好ましく、さらには 80 %以上にするのがより 好ましい。  In addition, a second base material holographic recording layer is laminated on a recording medium such as used in a holographic recording / reproducing apparatus described in JP-A-2002-123949, WO 99/57719, and the like. It is preferable that a reflection layer is provided on the surface or on the opposite surface. When such a reflection layer is provided, the reflectance is preferably set to 70% or more with respect to the wavelength of the light to be reflected. % Is more preferable.
このような反射層は、所望する反射率が得られれば特に材質に制限はないが、通 常、金属などの薄膜を基材表面に設けることにより積層することができる。例えば、 このような反射層を形成するためには真空蒸着法、イオンプレーティング法、スパ ッタリング法などの公知の方法によって金属薄膜として、金属の単結晶または多結 晶として積層することができ、金属薄膜を積層するために用いられる金属としては、 ァノレミ-ゥム、 亜鈴、 アンチモン、 インジウム、 セレン、 錫、 タンタノレ、 クロム、 鉛、 金、 銀、 白金、 ニッケル、 ニオブ、 ゲルマニウム、 珪素、 モリブデン、 マンガ ン、 タングステン、パラジウム等の金属を一種或いは二種以上併用などにより形成 することができる。 この金属薄膜層の厚みは、所望する反射率を得ることができれ ばどのような膜厚であっても構わないが、通常 1一 3 000 nmの範囲であり、好 ましくは 5— 2000 nmの範囲である。 The material of such a reflective layer is not particularly limited as long as a desired reflectance can be obtained. Normally, the layers can be laminated by providing a thin film of a metal or the like on the surface of the substrate. For example, to form such a reflective layer, it can be laminated as a metal thin film, a metal single crystal or a polycrystal by a known method such as a vacuum deposition method, an ion plating method, and a sputtering method, The metals used for laminating the metal thin film include anolemmium, dumbbell, antimony, indium, selenium, tin, tantalum, chromium, lead, gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, Metals such as manganese, tungsten, and palladium can be used alone or in combination of two or more. The thickness of the metal thin film layer may be any thickness as long as a desired reflectance can be obtained, but is usually in the range of 1 to 3 000 nm, preferably 5 to 2000 nm. nm range.
さらに、本発明のホログラフィック記録メディアにおいて、公知の CDや DVD 等の光記録ディスク同様に、記録される情報あるいは記録された情報がメディァの どの位置にあるかをトラッキングする為に、いずれかの基材の一方の面に物理的な パターンが形成されていても良く、このようなパターンあるいは形成方法としては、 例えば特開 200 3—1 7 84 5 6号、 同 2003-228 8 7 5号、 同 200 3 - 33 1464号、 同 2004— 1 26 03 8号、 同 20 04— 1 26040号、 同 2 004—1 26 04 1号、 同 2004-1 2 73 7 9号、 米国特許 6, 62 5, 1 0 0号、米国公開特許 2004/00423 75号、 同 2004/006 74 1 9号 等に記載されたものを適時選択して形成することができる。  Further, in the holographic recording medium of the present invention, similarly to the known optical recording disks such as CDs and DVDs, in order to track the information to be recorded or the position of the recorded information on the media, any one of them is used. A physical pattern may be formed on one surface of the substrate, and such a pattern or a forming method is described in, for example, JP-A-2003-178564, JP-A-2003-228885. No. 2003-33 1464, No. 2004-126306, No. 2004-126040, No. 2004-126041, No. 2004-1 273 79, No. 62, 100, U.S. Patent Publication No. 2004/0042375, 2004/006 7419, and the like can be appropriately selected and formed.
—方、ホログラフィック記録メディアにおいては、ホログラフィック記録層をで きるだけ厚くすることで、 高記憶容量の記録メディアを作製することができるが、 該記録メディアの使用環境や記録された情報の読み取り誤差などを考慮した場合、 本発明においては、第一の基材の厚みを D l、第二の基材の厚みを D 2、 ホロダラ フィック記録層の厚みを Dhとした際に、 0. 1 5≤DhZ (D 1 +D 2) ≤ 2. 0の関係を満たすことが好ましい。 On the other hand, in a holographic recording medium, a recording medium with a high storage capacity can be manufactured by making the holographic recording layer as thick as possible. In consideration of errors and the like, in the present invention, the thickness of the first base material is Dl, the thickness of the second base material is D2, Assuming that the thickness of the thick recording layer is Dh, it is preferable that the relationship of 0.15≤DhZ (D1 + D2) ≤2.0 is satisfied.
ここで、 0. 1 5 >Dh/ (D 1 +D 2) ではホログラフィック記録層の膜厚を 厚くできないし、或いはたとえ記録層の膜厚を厚くしたとしても基材の厚みが厚く なり、記録メディア全体が厚くなつてしまう。 この場合、記録メディア単体として の質量が重く装置の駆動系への負荷が生じる場合があることから好ましくない。ま た、 Dh/ (D 1 +D 2) > 2. 0の場合には、 記録層の膜厚を確保しつつ記録メ ディァの厚みを薄くすることは可能となるが、基材の厚みに対して記録層の膜厚が 厚くなり、記録メディアの面精度や使用環境温度における記録層の膜厚ムラ、不慮 の応力が掛かった際に記録層の膜厚変動、さらには第一の基材と第二の基材がずれ てしまう場合が有ることから好ましくない。  Here, at 0.15> Dh / (D1 + D2), the thickness of the holographic recording layer cannot be increased, or even if the thickness of the recording layer is increased, the thickness of the base material increases. The entire recording medium becomes thick. In this case, the mass of the recording medium alone is heavy, which may cause a load on the drive system of the apparatus, which is not preferable. When Dh / (D 1 + D 2)> 2.0, it is possible to reduce the thickness of the recording medium while securing the thickness of the recording layer. On the other hand, the thickness of the recording layer becomes thicker, the surface accuracy of the recording medium, the thickness unevenness of the recording layer at the operating temperature, the thickness fluctuation of the recording layer when unexpected stress is applied, and the first base material. And the second substrate may be displaced, which is not preferable.
さらに、ホログラフィック露光時のエネルギー損失の面から第一の基材の厚み D Further, from the viewpoint of energy loss during holographic exposure, the thickness of the first substrate D
1、第二の基材の厚み D 2の関係が D 1≤D 2であることが好ましく、また記録メ ディアの平面性を確保するためには D 1と D 2の厚みの比率としては 0. 20≤D 1/D 2≤ 1. 00の範囲にするのがより好ましい。 1, it is preferable that the relation between the thickness D2 of the second base material is D1≤D2, and in order to ensure the flatness of the recording medium, the ratio of the thickness of D1 to D2 is 0. More preferably, it is in the range of 20≤D1 / D2≤1.00.
また、ホログラフィック記録層の厚み D hとしては記録層の回折効率やダイナミ ックレンジ、 空間分解能などにより一概に決められないが、 通常 200 μπι以上、 Also, the thickness D h of the holographic recording layer cannot be determined unconditionally due to the diffraction efficiency, dynamic range, spatial resolution, etc. of the recording layer, but it is usually 200 μπι or more.
2. 0 mm以下であることが好ましく、 200 μ m未満では高記憶容量の記録メデ ィァを得ることができず、 2. 0mmよりも厚い場合には、記録メディアの面精度 や使用環境温度における記録層の厚みムラが生じる場合が有ることから好ましく なレ、。 If it is less than 200 μm, it is not possible to obtain a recording medium with a high storage capacity, and if it is thicker than 2.0 mm, the surface accuracy of the recording medium and the operating temperature It is not preferable because the recording layer may have uneven thickness.
—方記録メディアの形状としては、該記録メディアに使用されるホログラフイツ ク記録 ·再生装置に適したものであれば特に制限はないが、 例えば米国特許第 5, 7 1 9 , 6 9 1号、 特開 2 0 0 2 - 1 2 3 9 4 9号等に記載された装置に用いるも のであればディスク状をしたものが好ましく、国際公開第 9 9 5 7 7 1 9号など に記載された装置を用いるのであればカード状のものが好ましい。 The shape of the recording medium is not particularly limited as long as it is suitable for the holographic recording / reproducing apparatus used for the recording medium. For example, US Pat. Disc-shaped ones are preferred for use in the apparatus described in 711, 691, JP-A-2002-123939, etc., and International Publication No. If the device described in 719 is used, a card-like device is preferable.
上述で詳述した、記録メディアの作製する方法としては、セーフライト下で常温 或いは必要に応じて加温してホログラフィック記録用組成物を混合することによ りホログラフィック記録層形成組成物を調製し、ホログラフィック露光時の重合阻 害を押さえるために脱気した後に、第一の基材上に常温或いは必要に応じて加温し たホログラフィック記録層形成組成物を付し、次いで第二の基材を所定の記録層の 厚みとなるように気泡が入らないように貼合後、最後に端部を封止することにより 記録メディアを製造することができる。 また、セーフライト下で第一の基材と第二 の基材を所定の間隙を有するように型に固定し、常温或いは必要に応じて加温した ホログラフィック記録用組成物を気泡が入らないように射出成形もしくは気泡が 入らないように減圧吸引させることにより第一の基材と第二の基材間に充填し、最 後に端部を封止することにより記録メディアを作製することができる。 尚、 ここで 言うセーフライト下とは、光重合開始剤が活性となる光の波長をカットした状態で の作業を指す。  As described above in detail, a method for producing a recording medium includes mixing a holographic recording layer forming composition by mixing a holographic recording composition by heating at room temperature or, if necessary, under safelight. After being prepared and degassed to suppress polymerization inhibition at the time of holographic exposure, the holographic recording layer-forming composition at room temperature or, if necessary, heated, is applied to the first substrate, and then A recording medium can be manufactured by laminating the two base materials so that air bubbles do not enter so as to have a predetermined thickness of the recording layer, and finally sealing the end. Further, the first base material and the second base material are fixed to a mold under a safelight so as to have a predetermined gap, and the holographic recording composition heated at room temperature or heated as necessary does not allow bubbles to enter. As described above, the recording medium can be manufactured by filling the space between the first base material and the second base material by injection molding or suctioning under reduced pressure so that air bubbles do not enter, and finally sealing the end. . The term “under safelight” as used herein refers to an operation in a state where the wavelength of light at which the photopolymerization initiator becomes active is cut.
また、貼合により記録メディアを作製する場合には、ホログラフィック記録層形 成組成物を前述した第一の基材上ではなく、第二の基材上に付しても良いし、第一 及び第二の基材の両方に付しても良い。 さらに、第一の基材、 ホログラフィック記 録層及ぴ第二の基材の端部を封止する場合には、封止できるような湿分硬化型の接 着剤に代表される液状の封止材を架橋させ封止させても良いし、予めホログラフィ ック記録層が所定の膜厚を確保するためのリング上の端部封止材などを用いて封 止させても良い。 次に、 ホログラフィック記録メディアに情報を記録する方法について詳述する。 本発明のホログラフィック記録方法に於ける第一の態様は、上述で詳述したホロ グラフィック記録メディアに、ホログラフィック露光する以前にパインダー形成化 合物を反応させバインダーを形成させた後に、記録したい情報を基に第一基材側か ら情報光と参照光を入射させホログラフィック露光を行い、光重合開始剤を活性ィ匕 させ、この活性種によりェチレン性不飽和結合を有する化合物をホログラフィック 記録層内で拡散重合させることによりホログラフィック記録メディアに情報を記 録することを特徴としている。 When a recording medium is produced by lamination, the holographic recording layer forming composition may be applied to a second substrate instead of the first substrate described above, And the second base material. Further, when sealing the first base material, the holographic recording layer and the end of the second base material, the liquid base such as a moisture-curable adhesive capable of sealing is used. The sealing material may be crosslinked and sealed, or may be sealed in advance using an end sealing material on a ring for ensuring a predetermined thickness of the holographic recording layer. Next, a method for recording information on a holographic recording medium will be described in detail. In the first aspect of the holographic recording method of the present invention, it is desired to perform recording after reacting a binder-forming compound with the holographic recording medium described above in detail before the holographic exposure to form a binder. Based on the information, information light and reference light are incident from the first base material side and holographic exposure is performed to activate the photopolymerization initiator, and the compound having an ethylenic unsaturated bond by the active species is holographically exposed. It is characterized by recording information on holographic recording media by diffusion polymerization in the recording layer.
一般に厚膜の層を付す場合には希釈するための溶剤無しに記録層形成組成物を 調製するため、 固体或いは高粘度の組成物では、均一膜厚を得る或いは組成物調製 時に卷き込まれた気泡の除去が難しくなる。そのため、記録層形成組成物を調製し た際に常温または加温した状態で流動性が必要となる。この記録層形成組成物が特 に常温で液状でかつ低粘度の場合には、記録メディァとして平面性を確保するのが 難しかったり、ホログラフィック露光で情報を記録した後の、 エチレン性不飽和結 合を有する化合物により形成された重合体が記録層内で位置がずれてしまう可能 性が有るので好ましくない。 .  In general, when a thick film layer is formed, a recording layer forming composition is prepared without a solvent for dilution. For a solid or high-viscosity composition, a uniform film thickness is obtained or the composition is wound during preparation of the composition. It is difficult to remove air bubbles. Therefore, when the recording layer forming composition is prepared, fluidity is required at room temperature or in a heated state. In particular, when the recording layer forming composition is liquid at room temperature and has low viscosity, it is difficult to secure the flatness as a recording medium, or the ethylenically unsaturated bond after recording information by holographic exposure. It is not preferable because the polymer formed by the compound having a combination may be displaced in the recording layer. .
そこで、上述の必須成分を含有するホログラフィック記録メディアに対して、ホ ログラフィック露光の前にバインダー形成化合物を架橋させることによりパイン ダ一とし、平面性の確保とホログラフィック露光時に、エチレン性不飽和結合を有 する化合物を有する化合物が拡散重合することにより形成された重合体の、ホログ ラフィック記録層内での移動を防止させることができる。  Therefore, a binder is formed on the holographic recording medium containing the above-mentioned essential components by crosslinking the binder-forming compound before the holographic exposure. The polymer formed by diffusion polymerization of the compound having the compound having a saturated bond can be prevented from moving in the holographic recording layer.
上述のようにしてバインダーが形成された後で、記録したい情報を基にしたホロ グラフィック露光を行い、光重合開始剤を活性化させ、 この活性種によりエチレン 性不飽和結合を有する化合物を拡散重合させることによりホログラフィック記録 メディアに情報を記録することができる。 After the binder is formed as described above, holographic exposure is performed based on the information to be recorded, and the photopolymerization initiator is activated. Information can be recorded on a holographic recording medium by diffusing and polymerizing a compound having an unsaturated bond.
尚、本記録方法における上述のバインダーを形成させるための架橋反応は、反応 可^な官能基の組み合わせを全て架橋させても良いし、実技上支障の生じない範囲 で一部のみ架橋させても良い。 きらに、ホログラフィック記録メディアに情報を記 録後には、記録されたホログラフィック情報を固定化する目的で、光及び必要に応 じて加えられる熱により、記録層内に残存しているエチレン性不飽和結合を有する 化合物を光重合開始剤で光重合、および残存するパインダ一形成化合物の未架橋の 官能基同士を熱架橋させてしまうのが好ましい。 この場合、露光に用いる光は記録 メディア全体に一括露光させるのが好ましく、加熱する場合には一括露光前、一括 露光と同時或いは一括露光後のいずれであっても良いし、複数の加熱処理を組み合 わせても良い。  The crosslinking reaction for forming the above-mentioned binder in the present recording method may be performed by crosslinking all combinations of functional groups that can be reacted, or by crosslinking only a part of the combination within a range that does not cause a practical problem. good. After the information has been recorded on the holographic recording medium, the ethylenic acid remaining in the recording layer may be exposed to light and heat, if necessary, for the purpose of fixing the recorded holographic information. It is preferable that the compound having an unsaturated bond is photopolymerized with a photopolymerization initiator, and that the uncrosslinked functional groups of the remaining binder-forming compound are thermally crosslinked. In this case, it is preferable that the light used for exposure is exposed to the entire recording medium at a time. When heating is performed, the light may be applied before, at the same time as, or after the simultaneous exposure, or a plurality of heat treatments may be performed. They may be combined.
本発明のホログラフィック記録方法に於ける第二の態様は、上述で詳述したホ口 ダラフィック記録メディァに、記録したい情報を基に第一基材側から情報光と参照 光を入射させホログラフィック露光を行い、光重合開始剤を活性化させ、 この活性 種によりエチレン性不飽和結合を有する化合物を拡散重合させることによりホロ グラフィック記録メディァに情報を記録し、ホログラフィック記録メディァへの情 報記録が終了した後に、さらにホログラフィック記録メディァ全体に熱および光照 射を行うことにより記録された情報を安定化させることを特徴としている。  According to a second aspect of the holographic recording method of the present invention, an information light and a reference light are made to enter the holographic recording medium described above in detail from the first base material side based on the information to be recorded. Exposure to activate the photopolymerization initiator, record the information on the holographic recording medium by diffusing and polymerizing the compound having an ethylenically unsaturated bond with this active species, and record the information on the holographic recording medium After the recording is completed, the recorded information is stabilized by further performing heat and light irradiation on the entire holographic recording medium.
本態様は、前述の第一の態様とは異なり、記録層形成組成物を調製した際に、加 温した状態では流動するが常温では流動しなレ、組成物、或レ、は剪断応力が加わらな い限り常温ではゲル化、或いはチキソ性を有する記録層形成組成物により記録層が 形成されたホログラフィック記録メディアに対して有効な記録方法である。 このような記録メディアにおいては、該記録メディアの平面性の確保と、ェチレ ン性不飽和結合を有する化合物の拡散重合により形成された重合体の移動防止に 対して、実技上問題ないレベルにすることはできるが、 さらなる記録情報保存性を 向上させる目的で、ホログラフィック記録メディアに情報を記録し終えた後に、光 及び熱により、記録層内に残存しているエチレン性不飽和結合を有する化合物を光 重合開始剤で光重合、および残存するバインダ一形成化合物の未架橋の官能基同士 を熱架橋させてしまうのが好ましい。 この場合、上述の第一の態様と同様に露光に 用いる光は記録メディァ全体に一括露光させるのが好ましく、記録メディアを加熱 する場合は一括露光前、一括露光と同時或いは一括露光後のレ、ずれであっても良い し、 幾つかの加熱処理を組み合わせても良い。 This embodiment differs from the first embodiment described above in that, when the recording layer forming composition is prepared, the composition, which flows in a heated state but does not flow at room temperature, has a shear stress. This is an effective recording method for a holographic recording medium in which a recording layer is formed by a recording layer forming composition having a gelling or thixotropy at room temperature unless added. In such a recording medium, there is practically no problem in securing the flatness of the recording medium and preventing the movement of the polymer formed by diffusion polymerization of the compound having an ethylenically unsaturated bond. However, after the information has been recorded on the holographic recording medium, the compound having an ethylenically unsaturated bond remaining in the recording layer by light and heat, for the purpose of further improving the preservability of recorded information Is preferably photopolymerized with a photopolymerization initiator, and the uncrosslinked functional groups of the remaining binder-forming compound are thermally crosslinked. In this case, it is preferable that the light used for exposure is exposed to the entire recording medium at a time, as in the first embodiment described above. It may be a deviation or a combination of several heat treatments.
また、本発明の第一及び第二の態様の記録方法に用いられる、ホログラフィック 記録メディアを記録 ·再生する装置としては、 本発明の記録メディアに対して記 録 ·再生可能なものであれば特に制限はなく、 そのような記録 ·再生する装置とし ては、 例えば米国特許第 5, 71 9, 691号、 同 5， 838, 467号、 同 6， 163, 391号、 同 6， 414， 296号、 米国公開公報 2002—13614 3号、 特開平 9— 305978号、 同 10— 124872号、 同 1 1— 21 9540 号、 特開 2000— 98862号、 同 2000— 298837号、 同 2001— 23 169号、 同 2002— 83431号、 同 2002— 123949号、 同 2002— 123948号、 同 2003— 43904号、 国際公開第 99 / 57719号、 同 02Z05270号、同 02Z75727号等に記載されたもの挙げることができ る。  Further, as an apparatus for recording / reproducing a holographic recording medium used in the recording methods of the first and second aspects of the present invention, any apparatus capable of recording / reproducing on the recording medium of the present invention can be used. There is no particular limitation, and examples of such a recording and reproducing apparatus include, for example, U.S. Patent Nos. 5,719,691, 5,838,467, 6,163,391, 6,414, No. 296, U.S. Publication No. 2002-136143, JP-A-9-305978, JP-A-10-124872, JP-A-11-21 9540, JP-A-2000-98862, JP-A-2000-298837, JP-A-2001-23 No. 169, 2002-83431, 2002-123949, 2002-123948, 2003-43904, WO 99/57719, 02Z05270, 02Z75727, etc. Can be done.
上に述べた記録'再生する装置に用いられるレーザーとして光源としては、記録 メディア中の光重合開始剤を活性ィ匕しホログラフィック記録可能、及び記録された ホログラムを読み取ることのできるレーザー光源であれば特に制限なく用いるこ とができ、 このような光源としては青紫色領域の半導体レーザー、アルゴンレーザ 一、 H e— C d レーザー、周波数 2倍 Y A Gレーザー、 H e— N e レーザー、 K r レ 一ザ一、 近赤外領域の半導体レーザーなどを挙げることができる。 As a light source used as a laser for the above-described recording / reproducing apparatus, the photopolymerization initiator in the recording medium was activated to enable holographic recording, and that the recording was performed. Any laser light source that can read holograms can be used without particular limitation. Examples of such light sources are a semiconductor laser in the blue-violet region, an argon laser, a He—Cd laser, a frequency doubled YAG laser, He—Ne lasers, Kr lasers, semiconductor lasers in the near infrared region, and the like can be given.
また、記録前のホログラフィック記録メディアおよび記録された情報が少なく追 記する可能性が有るホログラフィック記録メディアは、通常ホログラフィック記録 に用いられる光源の波長を I n mとした際に、 （λ + 1 0 0 ) n m以下、 好ましく は（λ + 2 0 0 ) n m以下の光に対して少なくとも遮光できるケースやカセットな どに保管して置かれ、該記録メディアにレーザー光を露光し記録するときのみケー スゃカセットから取出し、遮光下でレーザー光を照射することにより情報が記録さ れる。  In addition, holographic recording media before recording and holographic recording media with little recorded information and with the possibility of additional recording, when the wavelength of the light source normally used for holographic recording is assumed to be I nm, (λ + When recording is performed by exposing the recording medium to laser light by exposing the recording medium to a case or cassette that can at least block light of 100 nm or less, preferably (λ + 200) nm or less. Only information is recorded by taking out the case ゃ from the cassette and irradiating it with a laser beam under light shielding.
さらに、本発明のホログラフィック記録方法により情報が記録された記録メディ ァは、前述した遮光できるケースやカセットなど力 ら取り出して、 C Dや D V Dな どと同様に明室で取り扱うことができるホログラフィック情報メディアとして使 用できる。 このホログラフィック情報メディアは、第一の基材と第二の基材の間に ホログラフィック情報記録層が挟持され、該ホログラフィック情報記録層が、イソ シァネート基を有する化合物と水酸基を有する化合物、イソシァネート基を有する 化合物とアミノ基を有する化合物、カルポジィミド基とカルボキシル基を有する化 合物、不飽和エステル基を有する化合物とアミノ基を有する化合物、不飽和エステ ル基を有する化合物とメルカブタン基を有する化合物、ビニル基を有する化合物と シリコンヒドリ ド基を有する化合物、ォキシラン基を有する化合物とメルカプタン 基を有する化合物、 並びに、 ォキシラン、 ォキセタン、 テトラヒドロフラン、 ォキ セパン、 単環ァセタール、 双環ァセタール、 ラタトン、 環状オルトエステル、 環状 カーボナートから選ばれた基を分子中に 1個以上有する化合物及ぴ熱カチオン重 合開始剤から選ばれる少なくとも一種のパインダ一形成化合物から形成されたパ インダーを主成分とする領域と、エチレン性不飽和結合を有する化合物を少なくと もモノマー単位として含むラジカル重合させて形成したラジカル重合体を主成分 とする領域とを有することを特徴としている。 なおこの場合、バインダーを主成分 とする領域とラジカル重合体を主成分とする領域との間で屈折差があることで情 報を読み取ることができ、例えば屈折率が 1 . 5 5以上であるエチレン性不飽和結 合を有する化合物を少なくともモノマー単位として含んでラジカル重合させて形 成したラジカル重合体を主成分とする領域に対して、バインダーを主成分とする領 域の屈折率は、前記ラジカル重合体を主成分とする領域の屈折率よりもバインダー を主成分とする領域の屈折率を低くすることことにより情報が記録されている。な お、 このホログラフィック情報メディアでは、通常の取り扱われる条件での情報が 記録された情報記録層に変化を生じにくい為、経時による再生装置での読み出し劣 化がほとんど無い。 Further, the recording medium on which information is recorded by the holographic recording method of the present invention can be taken out of a light-shielding case or cassette such as the above-mentioned light-shielding case, and can be handled in a light room like a CD or DVD. Can be used as information media. In this holographic information medium, a holographic information recording layer is sandwiched between a first base material and a second base material, and the holographic information recording layer has a compound having an isocyanate group and a compound having a hydroxyl group, A compound having an isocyanate group and a compound having an amino group, a compound having a carbodiimide group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a compound having a mercaptan group Compounds, compounds having a vinyl group and a compound having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxolane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, ratatone, Cyclic orthoester, ring Condition A region mainly composed of a binder formed of a compound having at least one compound selected from a carbonate and a compound having at least one group selected from carbonates and a thermal cation polymerization initiator; And a region mainly composed of a radical polymer formed by radical polymerization containing at least a compound having a saturated bond as a monomer unit. Note that in this case, information can be read because there is a difference in refraction between the region containing a binder as a main component and the region containing a radical polymer as a main component. For example, the refractive index is 1.55 or more. The refractive index of a region mainly containing a binder is higher than that of a region mainly containing a radical polymer formed by radical polymerization containing at least a compound having an ethylenically unsaturated bond as a monomer unit. Information is recorded by lowering the refractive index of the region mainly containing the binder than the refractive index of the region mainly containing the radical polymer. In this holographic information medium, the information recording layer on which information is recorded under normal handling conditions is unlikely to change, so that there is almost no deterioration in readout by the reproducing apparatus over time.
〔実施例〕  〔Example〕
以下に本発明の実施例を挙げて具体的に説明する力 S、本発明の実施態様はこれら の例に限定されるものではない。  The power S specifically described below with reference to examples of the present invention, and embodiments of the present invention are not limited to these examples.
尚、ホログラフィック記録層形成組成物を調製する際に用いたパインダ一形成化 合物 （A- 1— 1 3 )、 エチレン性不飽和結合を有する化合物 （B- 1— 1 0 )、 光重 ' 合開始剤 （C- 1一 5 )、 增感色素 （D- 1— 1 3 ) を以下に示す。  The binder-forming compound (A-1-1-3) used in preparing the holographic recording layer-forming composition, the compound having an ethylenically unsaturated bond (B-1-1-10), 'The combination initiator (C-115) and the dye (D-1-1-3) are shown below.
〈パインダ一形成化合物〉  <Pinder-forming compound>
(A - 1 ：イソシァネート基を有する化合物） 2 -イソシァネートェチルー 2， 6 - ジイソシァネートカプロエート（N C O含有量： 4 9 . 8質量0 /0、分子量： 2 5 3 . 2) . (A - 1: Compounds having Isoshianeto group) 2 - iso Xia sulfonates E Chiru 2, 6 - di iso Xia sulfonate caproate (NCO content: 4 9 8 mass 0/0, the molecular weight: 2 5 3. 2)
(A- 2 ：イソシァネート基を有する化合物） へキサメチレンジシシシァネート のポリイソシァネート体 （NCO含有量： 1 9. 7質量％ :旭化成 （株） 製、 デュ ラネート D- 101)  (A-2: a compound having an isocyanate group) Hexamethylene dissicinate polyisocyanate (NCO content: 19.7% by mass: duranate D-101, manufactured by Asahi Kasei Corporation)
(A-3 ：水酸基を有する化合物） グリセリンのポリプロピレンォキサイド付カロ 物 （平均分子量 1000 : 日本油脂 （株） 製、 ュ-オール TG- 1000)  (A-3: a compound having a hydroxyl group) Carohydrate of glycerin with polypropylene oxide (Average molecular weight: 1000: TG-1000, manufactured by NOF Corporation)
(A - 4) ウレタン硬化触媒 （日東化成 （株） 製、 ネオスタン U- 100) (A- 5) ポリプロピレンク"リコールジグリシジルエーテル (共栄社化学 (株) 製、 ェポライト 200 P)  (A-4) Urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) (A-5) Polypropylene glycol diglycidyl ether (Epolite 200P, manufactured by Kyoeisha Chemical Co., Ltd.)
(A-6：メルカプタン基を有する化合物） ペンタエリスリ トール （テトラキスメ ルカプトプロピオネート）  (A-6: Compound having a mercaptan group) Pentaerythritol (tetrakismercaptopropionate)
(A-7) 2， 4， 6—トリス (ジメチルアミノメチノレ) フエノール  (A-7) 2, 4, 6-tris (dimethylaminomethinole) phenol
(A-8 ：ォキセタン基を分子中に有する化合物） 3_ェチル -3- (フヱノキシメ チノレ） ォキセタン  (A-8: Compound having an oxetane group in the molecule) 3_ethyl-3- (phenyloxymethyl) oxetane
(A-9) 熱カチオン重合開始剤 （三新化学工業 （株） 製、 サンエイド S 1-45) (A-9) Thermal cationic polymerization initiator (San-Aid S 1-45 manufactured by Sanshin Chemical Industry Co., Ltd.)
(A— 10 ：イソシァネート基を有する化合物） 1， 8—ジイソシァネート一 4— ィソシァネートメチルーオタタン （N C 0含有量： 50. 2質量0 /0、 分子量： 25 1. 3) (A- 10: Isoshianeto compound having a group) 1, 8-Jiisoshianeto one 4-I Société § sulfonates methylcyclohexyl OTA Tan (NC 0 content: 50.2 mass 0/0, the molecular weight: 25 1.3)
(A-1 1 ：イソシァネート基を有する化合物） へキサメチレンジイソシァネー ト （NCO含有量： 50. 0質量％)  (A-11: compound having an isocyanate group) hexamethylene diisocyanate (NCO content: 50.0% by mass)
(A - 12 ：水酸基を有する化合物） ポリプロピレングリコール （平均分子量 1 000 : 日本油脂 （株） 製、 ュニオール D- 1000)  (A-12: a compound having a hydroxyl group) Polypropylene glycol (average molecular weight: 1 000: Uniol D-1000, manufactured by NOF Corporation)
(A - 13 ：水酸基を有する化合物） トリエチレングリコール （分子量 150. 2) (A-13: a compound having a hydroxyl group) triethylene glycol (molecular weight 150. 2)
〈エチレン性不飽和結合を有する化合物〉  <Compound having an ethylenically unsaturated bond>
(B-1) EO変性トリプロモフヱ二ルァクリレート （屈折率 * 1 = 1. 564 : 第一工業製薬 （株） 製、 ニューフロンティア BR- 31)  (B-1) EO-modified tripromophyl acrylate (refractive index * 1 = 1.564: New Frontier BR-31, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
(B— 2) ヒ ドロキシェチルイ匕 ;3—ナフトールアタリレート（屈折率 = 1. 583 : 新中村化学 （株） 製、 NKエステル A— NP - 1 E)  (B-2) Hydroxyshetilidani; 3-naphthol acrylate (refractive index = 1.583: Shin-Nakamura Chemical Co., Ltd., NK ester A- NP-1E)
(B - 3) 9, 9一ビス （4— (2 -アタリロイルォキシエトキシ） フエニル) フル オレン （屈折率 =1. 615 :大阪ガス （株） 製、 BPEFA)  (B-3) 9, 9-bis (4- (2-attaryloyloxyethoxy) phenyl) fluorene (refractive index = 1.615: Osaka Gas Co., Ltd., BPEFA)
' (B-4) フエノキシェチルァクリレート (屈折率 = 1. 519) '' (B-4) phenoxshetyl acrylate (refractive index = 1.519)
(B-5) 4-プロモスチレン （屈折率 =1. 594)  (B-5) 4-bromostyrene (refractive index = 1.594)
(B-6) ヒ ドロキシェチノレイ匕 0—フエニルフエノールアタリレート （屈折率 = 1. 576 ：新中村化学 （株） 製、 NKエステル A— L4)  (B-6) Hydroxishechinorei 0-phenylphenol acrylate (refractive index = 1.576: NK ester A-L4, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-7) パラクミルフエノキシエチレングリコールアタリ レート (屈折率 = 1. 553 :新中村化学 （株） 製、 NKエステル A— CMP-1 E)  (B-7) Paracumyl phenoxyethylene glycol acrylate (refractive index = 1.553: NK ester A—CMP-1 E, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-8) 9， 9—ビス （3—フエニル— 4—アタリロイルポリオキシエトキシ） フ ルオレン （屈折率 =1. 597 ：新中村化学 （株） 製、 NKエステル A- BPFL- 4 E)  (B-8) 9,9-bis (3-phenyl-4-atalyloylpolyoxyethoxy) fluorene (refractive index = 1.597: Shin-Nakamura Chemical Co., Ltd., NK ester A-BPFL-4E)
(B - 9) トリプロモフエ二ルアタリレート （屈折率 * 1 = 1. 567 ：第一ェ 業製薬 （株） 製、 ニューフロンティア BR— 30)  (B-9) Tripromophenyl atalylate (refractive index * 1 = 1.567: New Frontier BR-30 manufactured by Dai-ichi Kagaku Pharmaceutical Co., Ltd.)
(B-10) EO変性テトラプロモビスフエノール Aジメタクリ レート （屈折率 (B-10) EO-modified tetrapromobisphenol A dimethacrylate (refractive index
* 1 = 1. 564 :第一工業製薬 （株） 製、 ニューフロンティア BR— 42M) 尚、 屈折率 * 1はスチレン 50 %溶液として 25 °Cで測定した。 * 1 = 1.564: New Frontier BR-42M, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Note that the refractive index * 1 was measured at 25 ° C as a 50% styrene solution.
〈光重合開始剤、 增感色素〉 (C-l) チタノセン系光重合開始剤 （チパスぺシャリティケミカル （株） 製、 ィルガキュア— 784) <Photopolymerization initiator, sensitive dye> (Cl) titanocene photopolymerization initiator (IRGACURE-784, manufactured by Chipas Charity Chemical Co., Ltd.)
(C-2) ( 77 6—タメン） ( η 5—シクロペンタジェエル) 鉄 （1 +) へキサフル 才ロホスフエ一ト  (C-2) (776-tamen) (η5-cyclopentajeel) iron (1+) hexaflu
(C-3) ( η 6—クメン) (77 5—シクロペンタジェニル) 鉄 （1 +) へキサフル 才ロアンチモネ一ト  (C-3) (η 6-cumene) (77 5-cyclopentagenenyl) iron (1+) hexaflu
(C-4) (?7 6-ペリレン） 5—シクロペンタジェニル） 鉄 （1+) へキサフ ノレォロアンチモネ一ト  (C-4) (? 7 6-perylene) 5-cyclopentagenenyl) iron (1+) hexaf-noreloantimonate
(C - 5) ( 6_フルオレン） ( η 5—シクロペンタジェニル) 鉄 （1 +) へキサ フノレオ口アンチモネート (C-5) (6_fluorene) (η5-cyclopentagenenyl) iron (1+) hexanole antimonate
Figure imgf000038_0001
D-12
Figure imgf000039_0001
Figure imgf000038_0001
D-12
Figure imgf000039_0001
D-13
Figure imgf000039_0002
D-13
Figure imgf000039_0002
《ホログラフィック記録層形成組成物の調製》  << Preparation of holographic recording layer forming composition >>
(ホログラフィック記録層形成組成物 1 )  (Holographic recording layer forming composition 1)
セーフライト下で、 48. 92 gのバインダー形成化合物 （前出 A— 5) と 8. 74 gのバインダー形成化合物 （前出 A- 7) を混合し溶液 1を調製した。 別途調 製した 30. 00 gのバインダー形成化合物 （前出 A— 6) と 1 1. 67 gのェチ レン性不飽和結合を有する化合物 （前出 B- 5) とを含む溶液 Aを溶液 1に添加し た。 次いで 0. 670 gの光重合開始剤 （前出 C-1) を添加溶解した後に、 最後 に調製した組成物を窒素で脱空気を施した後、超音波洗浄器で内包されている気体 成分を除去し、 比較となるホログラフィック記録層形成組成物 1を調製した。  Solution 1 was prepared by mixing 48.92 g of the binder-forming compound (A-5 above) and 8.74 g of the binder-forming compound (A-7 above) under safelight. A solution A containing 30.00 g of a binder-forming compound (A-6 above) and 11.67 g of a compound having an ethylenically unsaturated bond (B-5) separately prepared as a solution. Added to 1. Next, after adding and dissolving 0.670 g of a photopolymerization initiator (C-1), the composition finally prepared was deaerated with nitrogen, and the gas components contained in the ultrasonic cleaning device were removed. Was removed, and a holographic recording layer forming composition 1 for comparison was prepared.
(ホログラフィック記録層形成組成物 2— 9)  (Holographic recording layer forming composition 2-9)
上述したホログラフィック記録層形成組成物 1において、エチレン性不飽和結合 を有する化合物、光重合開始剤を表 1に記載した化合物及び添加量に変更し、 さら に溶液 1に表 1に記載した添加量の増感色素を溶解した以外はホログラフィック 記録層形成組成物 1と同様な方法でホログラフィック記録層形成組成物 2— 9を 調製した。 【表 1 In the holographic recording layer forming composition 1 described above, the compound having an ethylenically unsaturated bond and the photopolymerization initiator were changed to the compounds and addition amounts shown in Table 1, and further added to the solution 1 as shown in Table 1. Holographic recording layer forming composition 2-9 was prepared in the same manner as holographic recording layer forming composition 1 except that the amount of sensitizing dye was dissolved. 【table 1
Figure imgf000040_0001
Figure imgf000040_0001
(ホログラフィック記録層形成組成物 10)  (Holographic recording layer forming composition 10)
セーフライト下で、 57. 82 gのバインダー形成化合物（前出 A- 3) に 36. Omgの 2, 6—ジ （ t—プチル） — 4—メチルフエノールと 67. lmgのウレタン 硬化触媒 （前出 A - 4) を混合溶解し溶液 2を調製した。 別途 7. 92 gのパイン ダー形成化合物（前出 A- 1), 23. 75 gのパインダ一形成化合物（前出 A- 2 ) 8. 00 gのエチレン性不飽和結合を有する化合物 （前出 B- 1) および 2. 00 gのエチレン性不飽和結合を有する化合物 （前出 B- 4) を混合溶解して溶液 Bを 調製し、 次いでこの溶液 Bに 0. 500 gの光重合開始剤 （前出 C- 1) を添加溶 解した後に、先に記載した溶液 2に添加し、最後に調製した組成物を窒素で脱空気 を施した後、超音波洗浄器で内包されている気体成分を除去し、比較となるホログ ラフィック記録層形成組成物 10を調製した。  Under safelight, 57.82 g of binder-forming compound (A-3 above) was added to 36. Omg of 2,6-di (t-butyl) —4-methylphenol and 67. lmg of urethane curing catalyst (previous Solution A-4) was mixed and dissolved to prepare solution 2. Separately, 7.92 g of a binder-forming compound (A-1), 23.75 g of a binder-forming compound (A-2) 8.00 g of a compound having an ethylenically unsaturated bond (see above) B-1) and 2.00 g of a compound having an ethylenically unsaturated bond (B-4) are mixed and dissolved to prepare a solution B. Then, 0.500 g of a photopolymerization initiator is added to the solution B. After adding and dissolving (C-1 above), add to solution 2 described above, deaerate the last prepared composition with nitrogen, and remove the gas contained in the ultrasonic cleaner. The components were removed, and a comparative holographic recording layer forming composition 10 was prepared.
(ホログラフィック記録層形成組成物 1 1— 24)  (Holographic recording layer forming composition 11-24)
上述したホログラフィック記録層形成組成物 10において、エチレン性不飽和結 合を有する化合物、光重合開始剤を表 2に記載した化合物及び添加量に変更し、 さ らに溶液 2に表 2に記載した'添加量の増感色素を溶解した以外はホログラフイツ ク記録層形成組成物 1 0と同様な方法でホログラフィック記録層形成組成物 1 1 24を調製した。 In the holographic recording layer forming composition 10 described above, the compound having an ethylenically unsaturated bond and the photopolymerization initiator were changed to the compounds and addition amounts shown in Table 2. Further, a holographic recording layer-forming composition 1 124 was prepared in the same manner as the holographic recording layer-forming composition 10 except that the sensitizing dye in the amount described in Table 2 was dissolved in Solution 2. .
【表 2】  [Table 2]
Figure imgf000041_0001
Figure imgf000041_0001
(ホログラフィック記録層形成組成物 25 )  (Holographic recording layer forming composition 25)
セーフライト下で、 89. 32 gのパインダー形成化合物 （前出 A- 8 9. 0 0 gのエチレン性不飽和結合を有する化合物 （前出 B_l 1. 00 gのエチレン 性不飽和結合を有する化合物 （前出 B- 4 0. 9 23 gの光重合開始剤 （前出 C - 2) および 9. 6mgの増感色素 （前出 D- 3) を混合溶解し溶液 Cを調製した。 この溶液 Cに 0. 1 79 gの熱カチオン重合開始剤 （前出 A- 9) を添加溶解し、 最後に調製した組成物を窒素で脱空気を施した後、超音波洗浄器で内包されている 気体成分を除去しホログラフィック記録層形成組成物 2 5を調製した。 Under safelight, 89.32 g of a binder-forming compound (A-8.90 g of a compound having an ethylenically unsaturated bond (B_l 1.00 g of a compound having an ethylenically unsaturated bond) (Solution B-0.93 g of photoinitiator (C-2 above) and 9.6 mg of sensitizing dye (D-3) were mixed and dissolved to prepare solution C. Add 0.179 g of thermal cationic polymerization initiator (A-9 above) to C, dissolve it, deaerate the last prepared composition with nitrogen, and enclose in an ultrasonic cleaner The gas component was removed to prepare a holographic recording layer forming composition 25.
(ホログラフィック記録層形成組成物 2 6— 3 0 )  (Holographic Recording Layer Forming Composition 26-30)
上述したホログラフィック記録層形成組成物 2 5において、エチレン性不飽和結 合を有する化合物、光重合開始剤及ぴ増感色素を'表 3に記載した化合物及び添加量 に変更した以外はホログラフィック記録層形成組成物 2 5と同様な方法でホ口グ ラフィック記録層形成組成物 2 6— 3 0を調製した。  In the holographic recording layer-forming composition 25 described above, except that the compound having an ethylenically unsaturated bond, the photopolymerization initiator, and the sensitizing dye were changed to the compounds and addition amounts shown in Table 3, A mouth graphic recording layer forming composition 26-30 was prepared in the same manner as the recording layer forming composition 25.
【表 3】  [Table 3]
Figure imgf000042_0001
Figure imgf000042_0001
(ホログラフィック記録層形成組成物 3 1—4 7 )  (Holographic recording layer forming composition 31-4-7)
セーフライト下で、表 4に示すィソシァネート化合物にエチレン性不飽和結合を 有する化合物を溶解し、次いでこの溶液に光重合開始剤を溶解させた。別途分子内 に 2個以上の水酸基を有する化合物に増感色素およびゥレタン硬化触媒（日東化成 (株） 製、 ネオスタン U- 1 0 0 ) を溶解させた溶液を、 この光重合開始剤を溶液 させた溶液に添加し、最後に調製した組成物を窒素で脱空気を施した後、真空脱気 で内包されている気体成分を除去し、ホログラフィック記録用組成物 3 1— 4 6を 調製した。 【表 4】 Under safelight, a compound having an ethylenically unsaturated bond was dissolved in the isocyanate compound shown in Table 4, and then a photopolymerization initiator was dissolved in this solution. Separately, a solution in which a sensitizing dye and a urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) are dissolved in a compound having two or more hydroxyl groups in the molecule is dissolved in the photopolymerization initiator. Holographic recording composition 31 1-46 was prepared by adding nitrogen to the solution and deaeration of the last prepared composition with nitrogen, and then removing the contained gas components by vacuum degassing. . [Table 4]
Figure imgf000043_0001
Figure imgf000043_0001
《ホログラフィック記録メディアの作製》 << Production of holographic recording media >>
(作製方法 1 )  (Preparation method 1)
第一の基材と第二の基材として、 厚み 0. 5mm (d l、 d 2) のガラスの片面 を 532 nmの波長に対して垂直な入射光による反射率が 0. 1%となるように反 射防止処理した。この第一の基材の反射防止処理していない面上に表 4に記載の記 録層の厚み（Dh) となるようにポリエチレンテレフタレートシートをスぺーサー とし、表 1一 3に記載したホログラフィック記録用組成物を第一の基材に付し、次 V、で第二の'基材の反射防止処理していない面をホログラフィック記録用組成物上 に空気層を卷き込まないように貼合しスぺーサーを介して第一の基材と第二の基 材を貼合させた。 最後に、端部を湿分硬ィ匕型の接着剤で封止し、表 5に記載した熱 処理条件で熱処理しホログラフィック記録メディアを作製した。 As a first substrate and a second substrate, one side of 0.5 mm (dl, d2) glass is made to have a reflectance of 0.1% with incident light perpendicular to the wavelength of 532 nm. Anti-reflection treatment was applied. A polyethylene terephthalate sheet was used as a spacer so that the recording layer thickness (Dh) shown in Table 4 was obtained on the surface of the first base material which had not been subjected to the antireflection treatment. Attach the graphic recording composition to the first substrate, and in the next V, do not wrap the air layer over the holographic recording composition on the non-reflective surface of the second 'substrate. And the first base material and the second base material were bonded via a spacer. Finally, the ends were sealed with a moisture-hardening adhesive, and heat-treated under the heat treatment conditions described in Table 5 to produce a holographic recording medium.
Figure imgf000045_0001
Figure imgf000045_0001
(作製方法 2 )  (Preparation method 2)
厚み 0. 5 mm (d 1) のガラスの片面を 532 nmの波長に対して垂直な入射 光による反射率が 0 . 1 %となるように反射防止処理を施すことにより第一の基材 を、厚み◦. 5 mm ( d 2 ) のガラスの片面を 5 3 2 n mの波長に対して垂直な入 射光による反射率が 9 0 %となるようにアルミ蒸着を施して第二の基材をそれぞ れ作製した。次いで、前述の第一の基材の反射防止処理していない面上に表 5記載 の記録層の厚み（D h ) となるようにポリエチレンテレフタレートシートをスぺー サ一とし、表 1一 3に記載したホログラフィック記録層形成組成物を第一の基材に 付し、次いで第二の基材のアルミ蒸着した面をホログラフィック記録用組成物上に 空気層を卷き込まないように貼合しスぺーサーを介して第一の基材と第二の基材 を貼合させた。最後に、端部を湿分硬化型の接着剤で封止し、表 6にに記載した熱 処理条件で熱処理しホログラフィック記録メディアを作製した。 One side of 0.5 mm (d 1) thick glass, perpendicular to 532 nm wavelength By subjecting the first substrate to anti-reflection treatment so that the reflectance by light becomes 0.1%, one side of the glass with a thickness of 5 mm (d 2) is exposed to a wavelength of 532 nm. The second substrates were each produced by performing aluminum vapor deposition so that the reflectance by vertical incident light became 90%. Next, a polyethylene terephthalate sheet was formed into a spacer so that the recording layer had a thickness (D h) shown in Table 5 on the surface of the first base material which had not been subjected to the anti-reflection treatment. The described holographic recording layer forming composition is applied to the first base material, and then the aluminum-deposited surface of the second base material is bonded onto the holographic recording composition so that an air layer is not wound. The first base material and the second base material were bonded via a spacer. Finally, the end was sealed with a moisture-curable adhesive, and heat-treated under the heat treatment conditions shown in Table 6 to produce a holographic recording medium.
【表 6】 [Table 6]
Figure imgf000047_0001
Figure imgf000047_0001
《ホログラフィック記録メディァへの記録及び評価》  《Recording and evaluation on holographic recording media》
(ホ口グラフィック記録メディァへの記録及ぴ評価 1 )  (Evaluation and evaluation of graphic recording media 1)
上述のようにして作製したホログラフィック記録メディアを遮光下で 5 0でで 1週間保存したののとしていないものとを、 米国特許第 5 7 1 9 , 6 9 1号に記 載の手順に従って、一連の多重ホログラムを書き込み、 下記の方法に従って、感度 (記録エネルギー） について測定、 評価を行い、 得られた結果を表 7に示した。 (感度の測定） According to the procedure described in U.S. Pat.No. 5,719,691, the holographic recording medium produced as described above was not stored under light shielding at 50 for 1 week. Write a series of multiplexed holograms, follow the method below (Recording energy) was measured and evaluated, and the obtained results are shown in Table 7. (Sensitivity measurement)
セーフライト下で 50°Cで 1週間保存していないホログラフィック記録メディ ァに、 Nd ： YAGレーザー （532 nm) を備えたホログラフィック作製装置に てデジタルパターンを表示し、 0. 1一 30mJ/c m 2のエネルギーで、 このデ ジタルパターン化されたホログラフィック露光することによりホログラムを得た。 次いで、 Nd ： Y AGレーザー （532 nm) を参照光に用いて、 発生した再生光 を CCDで読み取り、良好なデジタルパターンが再生できた最小露光量を感度（S 1 1 ) として測定した。 また、 50 で 1週間保存したホログラフィック記録メデ ィァを前述と同様の方法で評価し、良好なデジタルパターンが再生できた最小露光 量を感度 （S 12) として測定した。 A digital pattern is displayed on a holographic recording medium equipped with an Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight. Holograms were obtained by holographic exposure of this digitally patterned with an energy of cm 2 . Then, using a Nd: YAG laser (532 nm) as reference light, the generated reproduction light was read by a CCD, and the minimum exposure amount at which a good digital pattern was reproduced was measured as the sensitivity (S11). The holographic recording media stored at 50 for 1 week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S12).
【表 7】  [Table 7]
Figure imgf000048_0001
Figure imgf000048_0001
上表から、本発明の記録メディアは比較例に対し、保存前後において高感度であ ることが分かる。  From the above table, it can be seen that the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
(ホログラフィック記録メディァへの記録及ぴ評価 2 ) 上述のようにして作製したホログラフィック記録メディアを遮光下で 50°Cで 1週間保存したののとしていないものとを、米国特許第 5, 719， 691号に記 載の手順に従って、一連の多重ホログラムを書き込み、 下記の方法に従って、感度 (記録エネルギー） について測定、 評価を行い、 得られた結果を表 8に示した。 (Recording and evaluation of holographic recording media 2) The holographic recording medium produced as described above was stored at 50 ° C for 1 week in the absence of light, and a series of multiplexing was performed according to the procedure described in US Patent No. 5,719,691. The hologram was written, the sensitivity (recording energy) was measured and evaluated according to the following method, and the obtained results are shown in Table 8.
(感度の測定）  (Sensitivity measurement)
セーフライト下で 50°Cで 1週間保存していないホログラフィック記録メディ ァに、 Nd ： YAGレーザー （532 nm) を備えたホログラフィック作製装置に てデジタルパターンを表示し、 0. 1一 3 Om j/cm2のエネルギーで、 このデ ジタルパターン化されたホログラフィック露光することによりホログラムを得た。 次いで、ホログラフィック記録メディアを 7万ルクスのサンシャインフエードメ一 タ下で 5分間処理した後に 100°Cで 5分間加熱処理した。この処理された記録メ ディアをセーフライト下で Nd： YAGレーザー（532 nm)を参照光に用いて、 発生した再生光を C C Dで読み取り、良好なデジタルパターンが再生できた最小露 光量を感度 （S 21) として測定した。 また、 50°Cで 1週間保存したホログラフ ィック記録メディアを前述と同様の方法で評価し、良好なデジタルパターンが再生 できた最小露光量を感度 （S 22) として測定した。 A digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight. A hologram was obtained by holographic exposure with this digital patterned at an energy of j / cm 2 . Next, the holographic recording medium was treated under a 70,000 lux sunshine fader for 5 minutes, and then heated at 100 ° C. for 5 minutes. Using the Nd: YAG laser (532 nm) as a reference beam under safe light, the processed recording medium is read using a CCD to read the generated reproduction light, and the minimum exposure amount at which a good digital pattern can be reproduced is determined by the sensitivity ( S 21). The holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S22).
【表 8】 [Table 8]
Figure imgf000050_0001
Figure imgf000050_0001
上表から、本発明の記録メディアは比較例に対し、保存前後において高感度であ ることが分かる。  From the above table, it can be seen that the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
(ホログラフィック記録メディァへの記録及ぴ評価 3 )  (Recording and evaluation of holographic recording media 3)
上述のようにして作製したホログラフィック記録メディアを遮光下で 50°Cで 1週間保存したののとしていないものとを、 特開 2002-123949号に記載 の手順に従って、一連の多重ホログラムを書き込み、下記の方法に従って、感度（記 録エネルギー） について測定、 評価を行い、 得られた結果を表 9に示した。  According to the procedure described in JP-A-2002-123949, the holographic recording medium produced as described above was not stored for 1 week at 50 ° C under shading, and a series of multiple holograms were written. The sensitivity (recording energy) was measured and evaluated according to the following method, and the results obtained are shown in Table 9.
(感度の測定）  (Sensitivity measurement)
セーフライト下で 50°Cで 1週間保存していないホログラフィック記録メディ ァに、 Nd ： Y AGレーザー （532 nm) を備えたホログラフィック作製装置に てデジタルパターンを表示し、 0. 1— 30m jZcm2のエネルギーで、 このデ ジタルパターン化されたホログラフィック露光することによりホログラムを得た。 次いで、ホログラフィック記録メディアを 7万ルクスのサンシャインフ ドメ タ下で 5分間処理した後に 100°Cで 5分間加熱処理した。この処理された記録メ ディアをセーフライト下で Nd :YAGレーザー（532 nm)を参照光に用いて、 発生した再生光を C C Dで読み取り、良好なデジタノレパターンが再生できた最小露 光量を感度 （S 31) として測定した。 また、 50°Cで 1週間保存したホログラフ ィック記録メディアを前述と同様の方法で評価し、良好なデジタルパターンが再生 できた最小露光量を感度 （S 32) として測定した。 A digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight. A hologram was obtained by performing holographic exposure with this digital pattern at an energy of jZcm 2 . Next, the holographic recording medium was treated under a 70,000 lux sunshine dome for 5 minutes, and then heated at 100 ° C for 5 minutes. Using the Nd: YAG laser (532 nm) as a reference beam under safe light, the processed reproduction medium was read by a CCD and the minimum exposure required to reproduce a good digital photo pattern was obtained. The light intensity was measured as sensitivity (S31). The holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S32).
【表 9】  [Table 9]
Figure imgf000051_0001
Figure imgf000051_0001
上表から、本発明の記録メディアは比較例に対し、保存前後において高感度であ ることが分かる。  From the above table, it can be seen that the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
(ホログラフィック記録メディァへの記録及び評価 4 )  (Recording and evaluation on holographic recording media 4)
上述のようにして作製したホログラフィック記録メディアを遮光下で 50°Cで 1週間保存したものとしていないものとを、米国特許第 5, 719， 691号に記 載の手順に従って、一連の多重ホログラムを書き込み、 下記の方法に従って、感度 (記録エネルギー） について測定、 評価を行い、 得られた結果を表 10に示した。  A series of multiple holograms was prepared according to the procedure described in U.S. Pat. No. 5,719,691 to determine whether the holographic recording medium produced as described above was stored at 50 ° C. for 1 week in the dark. Was written, the sensitivity (recording energy) was measured and evaluated according to the following method, and the obtained results are shown in Table 10.
(感度の測定）  (Sensitivity measurement)
セーフライト下で 50°Cで 1週間保存していないホログラフィック記録メディ ァに、青紫色領域の半導体レーザー （405 nm) ^備えたホログラフィック作製 装置にてデジタルパターンを表示し、 0. 1 3 Om j/cm2のエネルギーで、 このデジタルパターン化されたホログラフィック露光することによりホログラム を得た。次いで、ホログラフィック記録メディアを 7万ルクスのサンシャインフエ ードメータ下で 5分間処理した後に 1 0 0 °Cで 5分間加熱処理した。この処理され た記録メディアをセーフライト下で青紫色領域の半導体レーザー（4 0 5 n m) を 参照光に用いて、発生した再生光を C C Dで読み取り、良好なデジタルパターンが 再生できた最小露光量を感度（S 4 1 ) として測定した。 また、 5 0 °Cで 1週間保 存したホログラフィック記録メディアを前述と同様の方法で評価し、良好なデジタ ルパターンが再生できた最小露光量を感度 （S 4 2 ) として測定した。 The digital pattern was displayed on a holographic recording medium that had not been stored at 50 ° C for 1 week under a safelight using a holographic manufacturing apparatus equipped with a blue-violet semiconductor laser (405 nm) ^. Hologram by this digitally patterned holographic exposure with energy of Om j / cm 2 Got. Next, the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes. The processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD. Was measured as the sensitivity (S41). The holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S42).
【表 1 0】  [Table 10]
Figure imgf000052_0001
Figure imgf000052_0001
上表から、本発明の記録メディアは比較例に対し、保存前後において高感度であ ることが分かる。 '  From the above table, it can be seen that the recording medium of the present invention has higher sensitivity before and after storage than the comparative example. '
(ホログラフィック記録メディァへの記録及び評価 5 )  (Recording and evaluation on holographic recording media 5)
上述のようにして作製したホログラフィック記録メディアを遮光下で 5 0 °Cで 1週間保存したものとしていないものとを、 特開 2 0 0 2- 1 2 3 9 4 9号に記載 の手順に従って、一連の多重ホログラムを書き込み、下記の方法に従って、感度（記 録エネルギー） について測定、 評価を行い、 得られた結果を 1 1に示した。  The holographic recording medium prepared as described above was not stored for 1 week at 50 ° C under shading, and the holographic recording medium was not stored according to the procedure described in Japanese Patent Application Laid-Open No. 2002-123939. Then, a series of multiple holograms were written, and the sensitivity (recording energy) was measured and evaluated according to the following method. The obtained results are shown in 11.
(感度の測定）  (Sensitivity measurement)
セーフライト下で 5 0 °Cで 1週間保存していないホログラフィック記録メディ ァに、青紫色領域の半導体レーザー （4 0 5 n m) を備えたホログラフィック作製 装置にてデジタルパターンを表示し、 0 . 1一 3 0 m j / c m2のエネルギーで、 このデジタルパターン化されたホログラフィック露光することによりホログラム を得た。次いで、 ホログラフィック記録メディアを 7万ルクスのサンシャインフエ ードメータ下で 5分間処理した後に 1 0 0 °Cで 5分間加熱処理した。この処理され た記録メディアをセーフライト下で青紫色領域の半導体レーザー（4 0 5 n m) を 参照光に用いて、発生した再生光を C C Dで読み取り、良好なデジタルパターンが 再生できた最小露光量を感度 （S 5 1 ) として測定した。 また、 5 0 °Cで 1週間保 存したホログラフィック記録メディアを前述と同様の方法で評価し、良好なデジタ ルパターンが再生できた最小露光量を感度 （S 5 2 ) として測定した。 Holographic recording with a blue-violet semiconductor laser (405 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight A digital pattern was displayed on the apparatus, and a hologram was obtained by performing holographic exposure with the digital pattern at an energy of 0.1 to 30 mj / cm 2 . Next, the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes. The processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD. Was measured as the sensitivity (S51). The holographic recording medium stored at 50 ° C. for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S52).
【表 1 1】 [Table 11]
Figure imgf000053_0001
Figure imgf000053_0001
上表から、本発明の記録メディアは比較例に対し、保存前後において高感度であ ることが分かる。  From the above table, it can be seen that the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
(ホログラフィック情報メディアの評価）  (Evaluation of holographic information media)
記録された情報を固定ィヒした表 8、表 9、表 1 0及び表 1 1で作製しホログラフ イツク情報メディァを下記の条件で保存し、保存前後で各情報メディアに合つた方 法でデジタルパターンを再生評価し、良好なデジタルパターンが再生できた最小露 光量の保存前後の差を以下の方法で評価し、 得られた結果を表 1 2に示した。  The holographic information media prepared in Table 8, Table 9, Table 10 and Table 11 in which the recorded information is fixed are stored under the following conditions, and before and after storage, digital data is created by a method suitable for each information medium. The patterns were reproduced and evaluated, and the difference between the minimum exposure light amount before and after storage at which a good digital pattern was reproduced was evaluated by the following method. The obtained results are shown in Table 12.
謹保存性） ホログラフィック情報メディアを 80°C、 2週間保存し、保存前後の最小露光感 度差 （ASh) を求めた。 Good preservation) The holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
最小露光感度差 (ASh) =保存後の最小露光感度 （S 2h) -保存前の最小露 光感度 （S 1 h)  Minimum exposure sensitivity difference (ASh) = Minimum exposure sensitivity after storage (S2h)-Minimum exposure sensitivity before storage (S1h)
(耐光保存性）  (Light storage stability)
温度 35°Cで、 7万ルクスのサンシャインフェードメータ下で 1週間保存、保存 前後の最小露光感度差 （ASw) を求めた。  The samples were stored at a temperature of 35 ° C under a sunshine fadeometer of 70,000 lux for 1 week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
最小露光感度差 （ASw) =保存後の最小露光感度 （S 2w) -保存前の最小露 光感度 （ S 1 w) Minimum exposure sensitivity difference (ASw) = Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
【表 1 2】 [Table 1 2]
Figure imgf000055_0001
Figure imgf000055_0001
上表から、本発明のホログラフィック情報メディアは、再生する為の感度低下も 無い良好な結果を示すことが分かる。  From the above table, it can be seen that the holographic information medium of the present invention shows good results without a decrease in sensitivity for reproduction.
(ホログラフィック記録メディァへの記録及び評価 6 )  (Recording and evaluation on holographic recording media 6)
上述のようにして作製したホログラフィック記録メディアを、米国特許第 5 7 1 9 6 9 1号明細書に記載の手順に従って、 一連の多重ホログラムを書き込み、 下記の方法に従って、 感度 （記録エネルギー）、 収縮耐性及び屈折率のコントラス トについて測定、 評価を行い、 得られた結果を表 1 3に示した。  The holographic recording medium produced as described above is written with a series of multiplexed holograms according to the procedure described in US Pat. No. 5,719,691, and the sensitivity (recording energy), The contraction resistance and the contrast of the refractive index were measured and evaluated, and the obtained results are shown in Table 13.
(感度の測定） セーフライト下でホログラフィック記録メディアに、 Nd ： Y AGレーザー （5 32 nm)を備えたホログラフィック作製装置にてデジタルパターンを表示し、 0. 1—3 Om j/c m 2のエネルギーで、 このデジタルパターン化されたホログラフ イツク露光することによりホログラムを得た。次いで、ホログラフィック記録メデ ィァを 7万ルクスのサンシャインフエ一ドメータ下で 5分間処理した後に 1 0 0°Cで 5分間加熱処理した。 この処理された記録メディアをセーフライト下で N d ： Y AGレーザー （532 nm) を参照光に用いて、発生した再生光を CCDで 読み取り、 良好なデジタルパターンが再生できた最小露光量を感度 （S 1) として 測定した。 (Sensitivity measurement) The holographic recording medium under safelight, Nd: Y AG laser (5 32 nm) to display the digital pattern in holographic manufacturing apparatus equipped with an energy of 0. 1-3 Om j / cm 2, the A hologram was obtained by digital pattern holographic exposure. Next, the holographic recording media was treated under a sunshine feed meter of 70,000 lux for 5 minutes and then heated at 100 ° C. for 5 minutes. Using the Nd: YAG laser (532 nm) as a reference beam, the read-out light generated is read by a CCD under safe light and the minimum exposure amount at which a good digital pattern can be reproduced is determined. (S1) was measured.
(収縮耐性の評価）  (Evaluation of shrinkage resistance)
収縮耐性は、 下記の方法により測定する収縮率で表示する。  The shrinkage resistance is indicated by a shrinkage rate measured by the following method.
図 1は、収縮率を測定する測定装置の原理を示す概略図である。 即ち、 ホロダラ ム 3を照明する白色照明光源の発光点を 01、観察者の視点を 02とする。測定装 置では、発光点 01に白色照明光源 4、視点 02に分光器 5が設置されている。 分 光器 5はバソコン 6に接続され、分光波長の輝度分布を測定するホログラム 3の上 面には、一部のみ光が透過するようなピンホール 8が孔設されている移動ピンホー ル板 7が設置されている。移動ピンホール板 7は、図示していない XYステージに 取り付けられて任意の位置に移動できる構成である。  FIG. 1 is a schematic diagram showing the principle of a measuring device for measuring a shrinkage ratio. That is, the emission point of the white illumination light source that illuminates the holo-drama 3 is 01, and the viewpoint of the observer is 02. In the measurement device, a white illumination light source 4 is installed at a light emitting point 01, and a spectroscope 5 is installed at a viewpoint 02. The spectrometer 5 is connected to a bass computer 6, and a moving pinhole plate 7 having a pinhole 8 through which only a part of light is transmitted is provided on the upper surface of the hologram 3 for measuring the luminance distribution of the spectral wavelength. Is installed. The movable pinhole plate 7 is configured to be attached to an XY stage (not shown) and move to an arbitrary position.
即ち、 移動ピンホール板 7が点 P (1、 J) にある場合、 ピンホール 8の中心か ら白色照明光源 4との角度を 0 c、分光器 5との角度を 0 iとする。ホログラム 3 の点 P (I, J) の領域は、 Θ cの角度から照明光 9で照明させ、 Θ iの方向に再 生光 1 1が出射する。再生光 11は分光器 5で分光され、輝度がピークとなる波長 が P (1、 J) での再生波長え cである。 この関係を用いて、 移動ピンホール板 7 を移動しながら、 ホログラム 3の各位置での e c、 e i、 を測定する。 That is, when the moving pinhole plate 7 is at the point P (1, J), the angle from the center of the pinhole 8 to the white illumination light source 4 is 0c, and the angle to the spectroscope 5 is 0i. The area of the point P (I, J) of the hologram 3 is illuminated with the illumination light 9 from the angle of Θc, and the reproduction light 11 is emitted in the direction of Θi. The reproduction light 11 is separated by the spectroscope 5 and the wavelength at which the luminance peaks is the reproduction wavelength c at P (1, J). Using this relationship, the moving pinhole plate 7 Measure e c , ei, at each position of hologram 3 while moving.
また、 点 P (1、 J) でのホログラムの収縮率を M (1、 J) とすると、 ホログ ラムの収縮率 M (1、 J) は、 記録前の光像記録材料の平均屈折率を n r、 現像処 理後のホログラムの平均屈折率を n cとすれば、 下式で表すことができる。  If the hologram shrinkage at point P (1, J) is M (1, J), the hologram shrinkage M (1, J) is the average refractive index of the optical image recording material before recording. Assuming that nr is the average refractive index of the hologram after the development processing is nc, it can be expressed by the following equation.
M ( I、 j =-n c/n r · L r ん c ' (c o s 6 c-c o s 0 i ) / ( c o s 0 o-c o s 0 r)  M (I, j = -n c / n rL r c '(cos 6 c-cos 0 i) / (cos 0 o-cos 0 r)
尚、上記式中 θ oはホログラフィック記録メディアへの入射角、 はレーザー 光の波長、 e rは参照光のホログラフィック記録メディアへの入射角である。  In the above equation, θo is the incident angle on the holographic recording medium, is the wavelength of the laser beam, and er is the incident angle of the reference light on the holographic recording medium.
(屈折率のコントラストの評価）  (Evaluation of contrast of refractive index)
屈折率のコントラストは、下記の方法に従って測定した回折効率より求めた。 回 折効率の測定は、 日本分光工業 （株）製の ART 25 C型分光光度計を用い、 幅 3 mmのスリットを有したフォトマルチメータを、試料を中心にした半径 20 cmの 円周上に設置した。 幅 0. 3mmの単色光を、 試料に対し 45度の角度で入射し、 試料からの回折光を検出した。正反射光以外で最も大きな値と、試料を置かず直接 入射光を受光した時の値との比を回折効率とし、得られたホログラムの回折効率か ら屈折率のコントラスト （Δη) を求めた。 The contrast of the refractive index was determined from the diffraction efficiency measured according to the following method. The diffraction efficiency was measured using an ART25C type spectrophotometer manufactured by JASCO Corporation. A photomultimeter with a 3 mm wide slit was placed on a 20 cm radius circle centered on the sample. It was installed in. Monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio of the largest value other than the specularly reflected light to the value when directly incident light is received without placing the sample is defined as the diffraction efficiency, and the refractive index contrast ( Δη ) is calculated from the diffraction efficiency of the obtained hologram. Was.
【表 13】 [Table 13]
Figure imgf000058_0001
Figure imgf000058_0001
上表から、 本発明の記録メディアは比較例に対し、 高感度、 低収縮率、 高コント ラストであり良好な結果を示すことが分かる。  From the above table, it can be seen that the recording medium of the present invention has high sensitivity, low shrinkage ratio, and high contrast as compared with the comparative example, and shows good results.
(ホログラフィック記録メディァへの記録及び評価 7 )  (Recording and evaluation on holographic recording media 7)
上述のようにして作製したホログラフィック記録メディアを、 特開 2002-1 Holographic recording medium produced as described above
23949号公報に記載の手順に従って、一連の多重ホログラムを書き込み、下記 の方法に従って、 感度 （記録エネルギー） について測定、 評価を行い、 得られた結 果を表 14に示した。 A series of multiplexed holograms was written according to the procedure described in JP 23949, and the sensitivity (recording energy) was measured and evaluated according to the following method. Table 14 shows the obtained results.
(感度の測定）  (Sensitivity measurement)
セーフライト下でホログラフィック記録メディアに、 Nd ： YAGレーザー （5 Nd: YAG laser (5
32 nm)を備えたホログラフィック作製装置にてデジタルパターンを表示し、 0. 1-3 Om jZcm2のエネルギーで、 このデジタノレパターン化されたホログラフ ィック露光することによりホログラムを得た。次いで、ホログラフィック記録メデ ィァを 7万ルクスのサンシャインフヱ一ドメータ下で 5分間処理した後に 1 0 0 °Cで 5分間加熱処理した。 この処理された記録メディアをセーフライト下で N d ： YA Gレーザー （5 3 2 n m) を参照光に用いて、発生した再生光を C C Dで 読み取り、 良好なデジタルパターンが再生できた最小露光量を感度 （S 1 ) として 測定した。 The digital pattern displayed by the holographic manufacturing apparatus equipped with a 32 nm), the energy of 0. 1-3 Om jZcm 2, which is the digital Honoré patterned holographic The hologram was obtained by performing a quick exposure. Next, the holographic recording media was treated under a sunshine feedmeter of 70,000 lux for 5 minutes and then heat-treated at 100 ° C. for 5 minutes. Using the Nd: YAG laser (532 nm) as a reference beam under safe light, this processed recording medium was read using a CCD to read out the generated reproduction light, and the minimum exposure amount at which a good digital pattern could be reproduced Was measured as the sensitivity (S 1).
【表 1 ,4】  [Table 1, 4]
Figure imgf000059_0001
Figure imgf000059_0001
上表から、評価 6を再現し、本発明の記録メディアは比較例に対し、高感度であ り良好な結果を示すことが分かる。  From the above table, it is found that the evaluation 6 is reproduced, and the recording medium of the present invention has high sensitivity and good results with respect to the comparative example.
(ホログラフィック情報メディアの評価）  (Evaluation of holographic information media)
記録された情報を固定化した表 1 3及び表 1 4で作成したホログラフィック情 報メディァを下記の条件で保存し、保存前後で各情報メディアに合つた方法でデジ タルパターンを再生評価し、良好なデジタルパターンが再生できた最小露光量の保 存前後の差を以下の方法で評価し、得られた結果を表 1 5に示した。 また、併せて ホログラフィック情報メディアの着色度合を下記の方法で評価し、得られた結果を 表 1 6に示した。 編保存性） The holographic information media created in Tables 13 and 14 in which the recorded information is fixed are stored under the following conditions, and before and after the storage, the digital pattern is reproduced and evaluated by a method suitable for each information medium. The difference between before and after the storage of the minimum exposure amount at which a good digital pattern was reproduced was evaluated by the following method, and the obtained results are shown in Table 15. In addition, the degree of coloring of the holographic information media was evaluated by the following method, and the obtained results are shown in Table 16. Knit preservation)
ホログラフィック情報メディアを 80 °C、 2週間保存し、保存前後の最小露光感 度差 （ASh) を求めた。  The holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
最小露光感度差 （Δ S h) =保存後の最小露光感度 （S 2 h) -保存前の最小露 光感度 （S 1 h)  Minimum exposure sensitivity difference (ΔSh) = Minimum exposure sensitivity after storage (S2h)-Minimum exposure sensitivity before storage (S1h)
(耐光保存性）  (Light storage stability)
温度 35°Cで、 7万ルクスのサンシャインフェードメータ下で 1週間保存、保存 前後の最小露光感度差 （ASw) .を求めた。  The samples were stored at a temperature of 35 ° C under a 70,000 lux sunshine fade meter for one week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
最小露光感度差 （ASw) =保存後の最小露光感度 （S 2w) -保存前の最小露 光感度 （S 1 w) Minimum exposure sensitivity difference (ASw) = Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
【表 1 5】 [Table 15]
Figure imgf000061_0001
Figure imgf000061_0001
上表から、本発明のホログラフィック情報メディアは比較例に対し、再生する為 の感度低下もなく保存性が良好な結果を示すことが分かる。  From the above table, it can be seen that the holographic information medium of the present invention shows good storage stability without lowering the sensitivity for reproduction as compared with the comparative example.
(着色度合の評価）  (Evaluation of coloring degree)
表 5で用いたホログラフィック記録メディアをホログラフィック露光せずに 7 万ルクスのサンシャインフェードメータ下で 5分間処理した後に、 1 0 0 °Cで 5分 間加熱処理しホログラフィック情報メディァを作成した。次いで下記の条件で保存 し、保存前後で各情報メディァの透過率を （株） 日立ハイテクノ口ジーズ製、 日立 分光光度計 U-4100で測定し、 以下の方法で評価した。 After treating the holographic recording media used in Table 5 without holographic exposure for 5 minutes under a sunshine fade meter of 70,000 lux, 5 minutes at 100 ° C A holographic information media was prepared by heating for a while. Then, it was stored under the following conditions, and before and after storage, the transmittance of each information medium was measured by Hitachi Spectrophotometer U-4100, manufactured by Hitachi High-Techno-Gee Corporation, and evaluated by the following method.
(耐熱保存性）  (Heat resistant storage)
ホログラフィック情報メディアを 80 °C、 2週間保存、保存前後の 400 n mの 透過率差 （ΔΤΙι) を求めた。  The holographic information media was stored at 80 ° C for 2 weeks, and the transmittance difference (ΔΤΙι) of 400 nm before and after storage was determined.
透過率差 （ATh) =保存前の透過率 （Tl h) -保存後の透過率 （T2h) (耐光保存性）  Transmittance difference (ATh) = Transmittance before storage (Tl h)-Transmittance after storage (T2h) (Light storage stability)
温度 35 で、 7万ルクスのサンシャインフェードメータ下で 1週間保存、保存 前後の 400 nmの透過率差 （ATh) を求めた。  Storage at a temperature of 35 under a 70,000 lux sunshine fademeter for one week, and the difference in transmittance (ATh) at 400 nm before and after storage was determined.
透過率差 （ATw) =保存前の透過率 （Tlw) -保存後の透過率 （T2w) Transmittance difference (ATw) = Transmittance before storage (Tlw)-Transmittance after storage (T2w)
【表 1 6】 [Table 16]
Figure imgf000063_0001
Figure imgf000063_0001
上表から、本発明のホログラフィック情報メディアは比較例に対し、着色も少な く保存性が良好な結果を示すことが分かる。 産業上の利用可能个生  From the above table, it can be seen that the holographic information medium of the present invention is less colored and shows better storage stability than the comparative example. Industrial Available Individuals
本発明により、感度が高く保存性に優れたホログラフィック記録メディァ、 ホロ グラフィック記録方法おょぴホログラフィック記録されたホログラフィック情報 メディアを得た。  According to the present invention, a holographic recording medium having high sensitivity and excellent preservability, a holographic recording method, and a holographic information medium recorded with holographic recording are obtained.

Claims

請求の範囲 The scope of the claims
1 . 第一基材と第二基材の間に、バインダ一形成化合物、 エチレン性不飽和結合 を有する化合物、前記エチレン性不飽和結合を有する化合物の重合反応を開始する ことのできる光重合開始剤、および、光重合開始剤を分光増感することができる増 感色素を含有するホログラフィック記録層を有するホログラフィック記録メディ ァにおいて、 1. A photopolymerization initiator capable of initiating a polymerization reaction between a binder-forming compound, a compound having an ethylenically unsaturated bond, and the compound having an ethylenically unsaturated bond between the first base material and the second base material. A holographic recording medium having a holographic recording layer containing a sensitizing dye capable of spectrally sensitizing a photopolymerization initiator.
前記バインダー形成化合物が以下の （1 )〜（8 ) から少なくとも 1つ選ばれる化 合物の組み合わせを含み、 The binder-forming compound contains a combination of at least one compound selected from the following (1) to (8):
( 1 ) イソシァネート基を有する化合物と水酸基を有する化合物、  (1) a compound having an isocyanate group and a compound having a hydroxyl group,
( 2 ) ィソシァネート基を有する化合物とアミノ基を有する化合物、  (2) a compound having an isocyanate group and a compound having an amino group,
( 3 ) カルポジイミド基とカルボキシル基を有する化合物、  (3) a compound having a carbodiimide group and a carboxyl group,
( 4 ) 不飽和エステル基を有する化合物とァミノ基を有する化合物、  (4) a compound having an unsaturated ester group and a compound having an amino group,
( 5 ) 不飽和エステル基を有する化合物とメルカプタン基を有する化合物、  (5) a compound having an unsaturated ester group and a compound having a mercaptan group,
( 6 ) ビニル基を有する化合物とシリコンヒドリ ド基を有する化合物、 (6) a compound having a vinyl group and a compound having a silicon hydride group,
( 7 ) ォキシラン基を有する化合物とメルカプタン基を有する化合物、  (7) a compound having an oxysilane group and a compound having a mercaptan group,
( 8 ) ォキシラン、 ォキセタン、 テトラヒドロフラン、 ォキセパン、 単環ァセター ル、 双環ァセタール、 ラタトン、 環状オルトエステル、 および環状カーボナートか ら選ばれた基を分子中に 1個以上有する化合物と、 熱カチオン重合開始剤、 前記エチレン性不飽和結合を有する化合物の含有量が組成物全体に対して 1一 5 0質量％の範囲であり、  (8) Initiation of thermal cationic polymerization with a compound having at least one group selected from oxysilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, ratatone, cyclic orthoester and cyclic carbonate in the molecule Agent, the content of the compound having an ethylenically unsaturated bond is in the range of 115% by mass with respect to the entire composition,
前記光重合開始剤が少なくとも下記一般式（1 ) で表される化合物を含有するこ とを特徴とするホログラフィック記録メディア。 一般式 ( 1 ) [A-F e -B ] + · X-The holographic recording medium, wherein the photopolymerization initiator contains at least a compound represented by the following general formula (1). General formula (1) [AF e -B] + X-
(式中 Aは、無置換またはアルキル基置換シクロペンタジェ-ル基、 Bは無置換ま た置換ァレーン基、 X—はフッ素原子を含有する対ァニオンを表す。 ) 2. 前記バインダ一形成化合物が、 (In the formula, A represents an unsubstituted or alkyl-substituted cyclopentagel group, B represents an unsubstituted or substituted arene group, and X— represents a fluorine atom-containing anion.) 2. The binder-forming compound But,
前記 ( 1 ) イソシァネート基を有する化合物と水酸基を有する化合物、 または 前記 （7 ) ォキシラン基を有する化合物とメルカブタン基を有する化合物 を含むことを特徴とする請求の範囲第 1項に記載のホログラフィック記録メデ ィァ。  The holographic recording according to claim 1, comprising (1) a compound having an isocyanate group and a compound having a hydroxyl group, or (7) a compound having an oxysilane group and a compound having a mercaptan group. Media.
3 . 前記バインダー形成化合物が、 前記 （1 ) イソシァネート基を有する化合物 と水酸基を有する化合物を含み、且つ前記ィソシァネート基を有する化合物は 3個 以上のイソシァネート基を化合物中 3 0質量％以上 6 5質量％以下となるように 含有することを特徴とする請求の範囲第 1項に記載のホログラフィック記録メデ ィァ。 3. The binder-forming compound contains (1) a compound having an isocyanate group and a compound having a hydroxyl group, and the compound having an isocyanate group has at least 30% by mass and at least 65% by mass of at least three isocyanate groups in the compound. %. The holographic recording medium according to claim 1, wherein the holographic recording medium is contained so as to be not more than%.
4 . イソシァネート基を有する化合物全体に対して、 3個以上のイソシァネート 基を化合物中 3 0質量％以上 6 5質量％以下となるように含有する前記ィソシァ ネート基を有する化合物が、 5— 1 0 0質量％以下含有していることを特徴とする 請求の範囲第 3項に記載のホログラフィック記録 4. The compound having an isocyanate group containing three or more isocyanate groups in an amount of 30% by mass or more and 65% by mass or less with respect to the whole compound having an isocyanate group is 5-10%. The holographic recording according to claim 3, wherein the content is 0% by mass or less.
5 . 前記イソシァネート基を有する化合物の分子量が、 2 0 0以上 5 0 0以下で あることを特徴とする請求の範囲第 3項に記載のホログラフィック記録メディア。 5. The holographic recording medium according to claim 3, wherein the compound having an isocyanate group has a molecular weight of not less than 200 and not more than 500.
6. 前記水酸基を有する化合物が、分子量 100以上 2000以下の分子内に 2 個以上の水酸基を有する化合物であることを特徴とする請求の範囲第 3項に記載 のホログラフィック記録メディア。 6. The holographic recording medium according to claim 3, wherein the compound having a hydroxyl group is a compound having a molecular weight of 100 or more and 2000 or less and having two or more hydroxyl groups in a molecule.
7. 前記エチレン性不飽和結合を有する化合物として、分子内に （メタ） ァクリ ロイル基を有する化合物を含んでいることを特徴とする請求の範囲第 1項に記載 のホログラフィック記録メディア。 8. 前記エチレン性不飽和結合を有する化合物として、 屈折率が少なくとも 1. 55以上の化合物を前記エチレン性不飽和結合を有する化合物全体に対して 50 質量％以上 100質量％以下含有することを特徴とする請求の範囲第 1項に記載 のホログラフィック記録メディア。 7. The holographic recording medium according to claim 1, wherein the compound having an ethylenically unsaturated bond includes a compound having a (meth) acryloyl group in a molecule. 8. As the compound having an ethylenically unsaturated bond, a compound having a refractive index of at least 1.55 or more is contained in an amount of 50% by mass or more and 100% by mass or less based on the whole compound having an ethylenically unsaturated bond. The holographic recording medium according to claim 1, wherein:
9. 前記ホログラフィック記録メディアの、前記第一基材の厚みを D 1、前記第 二基材の厚みを D 2、および前記ホログラフィック記録層の厚みを Dhとし、前記 ホログラフィック記録層の厚み Dhが 200 μιη以上 2. 0 mm以下、 0. 15≤ Dh/ (D 1+D2) ≤ 2. 0、 かつ D 1 2の関係を満たすことを特徴とする 請求の範囲第 1項に記載のホログラフィック記録メディァ。 9. In the holographic recording medium, the thickness of the first base material is D1, the thickness of the second base material is D2, and the thickness of the holographic recording layer is Dh, and the thickness of the holographic recording layer is Dh is 200 μιη or more and 2.0 mm or less, 0.15≤Dh / (D 1 + D2) ≤2.0, and satisfies the relationship of D 12 2. Claim 1. Holographic recording media.
10. 前記第一基材が透明であり、 前記第一基材においてホログラフィック記録 層に接する面とは反対の面に反射防止処理がなされていることを特徴とする請求 の範囲第 1項に記載のホログラフィック記録メディァ。 10. The first substrate according to claim 1, wherein the first substrate is transparent, and an antireflection treatment is performed on a surface of the first substrate opposite to a surface in contact with the holographic recording layer. The described holographic recording media.
1 1 . 前記第一基材の材質がガラスであることを特徴とする請求の範囲第 1項に 記载のホログラフィック記録メディア 1 2 . 前記第二基材に反射率が 7 0 %以上の反射層が積層されていることを特徴 とする請求の範囲第 1項に記載のホログラフィック記録メディァ。 11. The holographic recording medium according to claim 1, wherein the material of the first base material is glass. 12. The second base material has a reflectance of 70% or more. 2. The holographic recording medium according to claim 1, wherein a reflective layer is laminated.
1 3 . 前記ホログラフィック記録メディアの形状がディスク状またはカード状で あることを特徴とする請求の範囲第 1項に記載のホログラフィック記録メディァ。 13. The holographic recording medium according to claim 1, wherein the holographic recording medium has a disk shape or a card shape.
1 4 . 請求の範囲第 1項に記載のホログラフィック記録メディアに記録する方法 において、前記ホログラフィック記録メディアにホログラフィック露光する以前に バインダー形成化合物を反応させバインダーを形成させた後に、記録したい情報を 基に第一基材側から情報光と参照光を入射させホログラフィック露光を行い、光重 合開始剤を活性化させ、この活性種によりエチレン性不飽和結合を有する化合物を ホログラフィック記録層内で拡散重合させることによりホログラフィック記録メ ディアに情報を記録することを特徴とするホログラフィック記録方法。 14. The method for recording on a holographic recording medium according to claim 1, wherein the information to be recorded after a binder-forming compound is reacted and a binder is formed before the holographic recording medium is subjected to holographic exposure. Holographic exposure is performed by injecting information light and reference light from the first base material side based on the holographic recording layer to activate the photopolymerization initiator. A holographic recording method, wherein information is recorded on a holographic recording medium by diffusion polymerization in a medium.
1 5 . 前記ホログラフィック記録方法において、 ホログラフィック記録メディア への情報記録が終了した後に、さらにホログラフィック記録メディア全体に熱およ ぴ光照射により安定化させることを特徴とする請求の範囲第 1 4項に記載のホロ 記録方法。 15. The holographic recording method, wherein after the information recording on the holographic recording medium is completed, the entire holographic recording medium is further stabilized by irradiation of heat and light. Holo recording method described in paragraph 4.
1 6 . 請求の範囲第 1項に記載のホログラフィック記録メディアに記録する方法 において、前記ホログラフィック記録メディアに記録したい情報を基に第一基材側 から情報光と参照光を入射させホログラフィック露光を行！/、、光重合開始剤を活性 ィ匕させ、この活性種によりエチレン性不飽和結合を有する化合物を拡散重合させる ことによりホログラフィック記録メディアに情報を記録し、ホログラフィック記録 メディアへの情報記録が終了した後に、さらにホログラフィック記録メディア全体 に熱および光照射を行うことにより記録された情報を安定化させることを特徴と するホログラフィック記録方法。 16. The method for recording on a holographic recording medium according to claim 1, wherein information light and reference light are incident from the first base material side based on information to be recorded on the holographic recording medium. Do exposure! /, Activating the photopolymerization initiator and diffusing and polymerizing a compound having an ethylenically unsaturated bond with the active species, thereby recording information on the holographic recording medium, and recording information on the holographic recording medium. A holographic recording method characterized by further stabilizing recorded information by irradiating the entire holographic recording medium with heat and light after completion.
1 7 . 請求の範囲第 1項に記載のホログラフィック記録メディアにおけるホログ ラフィック記録層に情報が記録されたホログラフィック情報記録層が積層された ホログラフィック情報メディァにおいて、該ホログラフィック情報記録層は、該バ ィンダー形成化合物から形成されたバインダーを主成分とする領域と、ェチレン性 不飽和結合を有する化合物を少なくともモノマー単位として含むラジカル重合さ せて形成したラジカル重合体を主成分とする領域とを有することを特徴とするホ ログラフィック情報メディァ。 17. A holographic information recording layer in which information is recorded on a holographic recording layer in the holographic recording medium according to claim 1, wherein the holographic information recording layer is A region mainly composed of a binder formed from the binder-forming compound and a region mainly composed of a radical polymer formed by radical polymerization containing at least a monomer unit containing a compound having an ethylenic unsaturated bond. A holographic information media characterized by having.
PCT/JP2004/013591 2003-09-17 2004-09-10 Holographic recording medium, holographic recording method, and holographic information medium WO2005029201A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04773235A EP1666988A4 (en) 2003-09-17 2004-09-10 Holographic recording medium, holographic recording method, and holographic information medium

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2003323809 2003-09-17
JP2003-323809 2003-09-17
JP2003396737 2003-11-27
JP2003-396737 2003-11-27
JP2004058640A JP2005181953A (en) 2003-11-27 2004-03-03 Holographic recording medium, holographic recording method, and holographic information medium
JP2004-58640 2004-03-03
JP2004-72139 2004-03-15
JP2004072139A JP4466141B2 (en) 2003-09-17 2004-03-15 Holographic recording composition, holographic recording medium, holographic recording method, and holographic information medium

Publications (1)

Publication Number Publication Date
WO2005029201A1 true WO2005029201A1 (en) 2005-03-31

Family

ID=34279972

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/013591 WO2005029201A1 (en) 2003-09-17 2004-09-10 Holographic recording medium, holographic recording method, and holographic information medium

Country Status (3)

Country Link
US (1) US20050058911A1 (en)
EP (1) EP1666988A4 (en)
WO (1) WO2005029201A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006018986A1 (en) * 2004-08-18 2006-02-23 Konica Minolta Medical & Graphic, Inc. Holographic recording medium, holographic recording method and holographic information medium

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004287138A (en) * 2003-03-24 2004-10-14 Konica Minolta Holdings Inc Composition for holographic recording, holographic recording medium and its recording method
WO2004090646A1 (en) * 2003-04-09 2004-10-21 Konica Minolta Medical & Graphic, Inc. Holographic recording medium and recording method using the same
JP2005275273A (en) * 2004-03-26 2005-10-06 Fuji Photo Film Co Ltd Hologram recording material, hologram recording method, and optical recording medium
WO2005109114A1 (en) * 2004-05-10 2005-11-17 Konica Minolta Medical & Graphic, Inc. Holographic recording medium, holographic recording method, and holographic information medium
KR100544824B1 (en) * 2005-01-27 2006-01-24 주식회사 코오롱 A composition for making of prism layer and prism film made by using the same
JP2006235386A (en) * 2005-02-25 2006-09-07 Fuji Photo Film Co Ltd Hologram recording material and optical recording material using the same
JP2007264091A (en) * 2006-03-27 2007-10-11 Toshiba Corp Hologram recording medium
EP1840652A1 (en) * 2006-03-27 2007-10-03 SeeReal Technologies S.A. Photo-curable resins and resin compositions with very high refractive indices for application in plastic optics
JP5130230B2 (en) * 2007-02-05 2013-01-30 新日鉄住金化学株式会社 Volume phase hologram recording material and optical information recording medium
CA2683905A1 (en) * 2007-04-11 2008-10-23 Bayer Materialscience Ag Advantageous recording media for holographic applications
JP2008304807A (en) * 2007-06-11 2008-12-18 Fujifilm Corp Composition for optical recording, holographic recording medium and information recording and reproducing method
JP2009048066A (en) * 2007-08-22 2009-03-05 Fujifilm Corp Holographic recording medium and device
EP2042528B1 (en) * 2007-09-25 2010-06-16 Sony Chemical & Information Device Corporation Curable resin composition
US7629264B2 (en) * 2008-04-09 2009-12-08 International Business Machines Corporation Structure and method for hybrid tungsten copper metal contact
CA2738835A1 (en) * 2008-10-01 2010-04-08 Bayer Materialscience Ag Prepolymer-based polyurethane formulations for producing holographic media
IL200722A0 (en) * 2008-10-01 2010-06-30 Bayer Materialscience Ag Photopolymer compositions for optical elements and visual displays
JP2012504777A (en) * 2008-10-01 2012-02-23 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト Media for volume holography based on self-developing polymers
CN102574877B (en) * 2009-11-03 2016-04-20 拜尔材料科学股份公司 Urethane acrylates with high refractive index and reduced double bond density
EP2450893A1 (en) * 2010-11-08 2012-05-09 Bayer MaterialScience AG Photopolymer formula for producing of holographic media with highly networked matrix polymers
TWI557187B (en) * 2012-05-03 2016-11-11 拜耳材料科學股份有限公司 Novel photoinitiators for photopolymers
EP3134446B1 (en) * 2014-04-25 2019-04-24 Covestro Deutschland AG Aromatic glycol ethers as co-monomers in holographic photopolymer formulas
KR102009421B1 (en) * 2017-04-25 2019-08-12 주식회사 엘지화학 Photopolymer composition
KR102157366B1 (en) * 2017-12-15 2021-03-29 주식회사 엘지화학 Dye compound and photopolymer composition
CN109100916A (en) * 2018-07-19 2018-12-28 江苏博砚电子科技有限公司 A kind of high-performance color photosensitive polymer combination and preparation method thereof
US11718580B2 (en) * 2019-05-08 2023-08-08 Meta Platforms Technologies, Llc Fluorene derivatized monomers and polymers for volume Bragg gratings
US11780819B2 (en) 2019-11-27 2023-10-10 Meta Platforms Technologies, Llc Aromatic substituted alkane-core monomers and polymers thereof for volume Bragg gratings
US11879024B1 (en) 2020-07-14 2024-01-23 Meta Platforms Technologies, Llc Soft mold formulations for surface relief grating fabrication with imprinting lithography

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01152109A (en) * 1987-12-09 1989-06-14 Toray Ind Inc Photopolymerizable composition
JPH11352303A (en) * 1998-03-24 1999-12-24 Lucent Technol Inc Optical product and its production
JP2002149043A (en) * 2000-11-10 2002-05-22 Fuji Photo Film Co Ltd Hologram recording medium and method of manufacturing volume phase type hologram using the same
JP2003156992A (en) * 2001-08-27 2003-05-30 Dainippon Printing Co Ltd Photosensitive composition for volume hologram recording and photographic medium for volume hologram recording using the same

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0152377B1 (en) * 1984-02-10 1987-12-09 Ciba-Geigy Ag Curable compositions and their use
US5886101A (en) * 1988-03-02 1999-03-23 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
US6017681A (en) * 1992-11-09 2000-01-25 Fujitsu Limited Method of coupling optical parts and method of forming a mirror
CA2176931A1 (en) * 1994-09-21 1996-03-28 Tsuguo Yamaoka Photopolymerizable composition containing squarylium compound
US6103454A (en) * 1998-03-24 2000-08-15 Lucent Technologies Inc. Recording medium and process for forming medium
HU9801029D0 (en) * 1998-05-05 1998-06-29 Optilink Ab Method and system for recording information on a holographic card
US6627354B1 (en) * 1999-03-01 2003-09-30 Lucent Technologies Inc. Photorecording medium, process for fabricating medium, and process for holography using medium
JP2001006215A (en) * 1999-06-22 2001-01-12 Mitsubishi Chemicals Corp Three-dimensional optical recording medium
JP2001089639A (en) * 1999-09-24 2001-04-03 Mitsubishi Heavy Ind Ltd Energy ray-curing resin composition
JP3655819B2 (en) * 2000-08-07 2005-06-02 株式会社オプトウエア Optical information recording apparatus and method, optical information reproducing apparatus and method, and optical information recording and reproducing apparatus and method
JP3639212B2 (en) * 2000-12-11 2005-04-20 株式会社オプトウエア Optical information recording method
JP4068809B2 (en) * 2001-02-01 2008-03-26 富士フイルム株式会社 Photopolymerizable composition and recording material
US7361432B2 (en) * 2001-02-01 2008-04-22 National Institute Of Advanced Industrial Science And Technology Composition for hologram-recording material, hologram-recording medium, and process for producing the same
US20030052311A1 (en) * 2001-07-06 2003-03-20 Yoshio Inagaki Two-photon absorption composition
US6743552B2 (en) * 2001-08-07 2004-06-01 Inphase Technologies, Inc. Process and composition for rapid mass production of holographic recording article
US6765061B2 (en) * 2001-09-13 2004-07-20 Inphase Technologies, Inc. Environmentally durable, self-sealing optical articles
US7074546B2 (en) * 2002-06-24 2006-07-11 Konica Corporation Light sensitive planographic printing plate precursor and its processing method
US6864019B2 (en) * 2002-06-27 2005-03-08 Imation Corp. Recording material formulations for holographic media
JP2005274587A (en) * 2002-08-14 2005-10-06 Konica Minolta Holdings Inc Optical image recording material, and recording method thereof and manufacturing method thereof
US7244532B2 (en) * 2002-10-07 2007-07-17 Tdk Corporation Holographic recording medium
JP2004287138A (en) * 2003-03-24 2004-10-14 Konica Minolta Holdings Inc Composition for holographic recording, holographic recording medium and its recording method
WO2004090646A1 (en) * 2003-04-09 2004-10-21 Konica Minolta Medical & Graphic, Inc. Holographic recording medium and recording method using the same
JP4325276B2 (en) * 2003-05-28 2009-09-02 コニカミノルタエムジー株式会社 Holographic recording medium and manufacturing method thereof
WO2005109114A1 (en) * 2004-05-10 2005-11-17 Konica Minolta Medical & Graphic, Inc. Holographic recording medium, holographic recording method, and holographic information medium
US20050286386A1 (en) * 2004-06-29 2005-12-29 Edwards Jathan D Dichroic coating for holographic data storage media
JPWO2006018986A1 (en) * 2004-08-18 2008-05-08 コニカミノルタエムジー株式会社 Holographic recording medium, holographic recording method, and holographic information medium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01152109A (en) * 1987-12-09 1989-06-14 Toray Ind Inc Photopolymerizable composition
JPH11352303A (en) * 1998-03-24 1999-12-24 Lucent Technol Inc Optical product and its production
JP2002149043A (en) * 2000-11-10 2002-05-22 Fuji Photo Film Co Ltd Hologram recording medium and method of manufacturing volume phase type hologram using the same
JP2003156992A (en) * 2001-08-27 2003-05-30 Dainippon Printing Co Ltd Photosensitive composition for volume hologram recording and photographic medium for volume hologram recording using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1666988A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006018986A1 (en) * 2004-08-18 2006-02-23 Konica Minolta Medical & Graphic, Inc. Holographic recording medium, holographic recording method and holographic information medium

Also Published As

Publication number Publication date
EP1666988A1 (en) 2006-06-07
EP1666988A4 (en) 2007-04-11
US20050058911A1 (en) 2005-03-17

Similar Documents

Publication Publication Date Title
WO2005029201A1 (en) Holographic recording medium, holographic recording method, and holographic information medium
JP5495238B2 (en) Advantageous recording medium for holographic applications
US20060040185A1 (en) Holographic recording medium, holographic recording method and holographic information medium
WO2005109114A1 (en) Holographic recording medium, holographic recording method, and holographic information medium
WO2008123612A2 (en) Volume holographic data recording media
KR20080028916A (en) Volume phase hologram recording material, process for producing the same, and recorded material
US20040197670A1 (en) Holographic recording medium and recording method thereof
KR20060110365A (en) Volume hologram recording material and volume hologram recording medium
JP4466140B2 (en) Holographic recording medium, holographic recording method, and holographic information medium
JP4874689B2 (en) Holographic recording composition and optical recording medium using the same
JP4466141B2 (en) Holographic recording composition, holographic recording medium, holographic recording method, and holographic information medium
WO2004090646A1 (en) Holographic recording medium and recording method using the same
JP4874854B2 (en) Holographic recording composition and holographic recording medium
JP5179250B2 (en) Optical recording composition and holographic recording medium
JP2005181954A (en) Holographic recording medium, holographic recording method, and holographic information medium
JP2007058992A (en) Optical recording meth0d, optical recording device, optical recording medium, and optical recording/reproducing method
JP2005181953A (en) Holographic recording medium, holographic recording method, and holographic information medium
JP4525042B2 (en) Holographic recording composition, holographic recording medium, and holographic recording method
JP2007272044A (en) Composition for optical recording, and optical recording medium using the same
JP2005043862A (en) Holographic recording composition, holographic recording medium and recording method thereof
US20050213486A1 (en) Optical recording medium and manufacturing method thereof
JP6048078B2 (en) Composition for hologram recording medium, hologram recording medium using the same, and method for producing them
JP2006065963A (en) Optical information recording medium
JP2005077940A (en) Hologram recording material and medium
JPWO2008123303A1 (en) Composition for fluorine-containing volume hologram optical information recording material and fluorine-containing volume hologram optical information recording medium using the same

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GE GM HR HU ID IL IN IS KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NA NI NO NZ OM PG PL PT RO RU SC SD SE SG SK SL SY TM TN TR TT TZ UA UG UZ VC VN ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IT MC NL PL PT RO SE SI SK TR BF CF CG CI CM GA GN GQ GW ML MR SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2004773235

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2004773235

Country of ref document: EP